OxyChem

Caustic Soda
Handbook 1 of 44

Caustic Soda
Handbook
Page

• Introduction & Principal Uses . . . . . . . . . . . . . . . . .2

• Manufacturing . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3

• Methods of Shipping Caustic Soda . . . . . . . . . . . .4

• Safety in Handling Caustic Soda . . . . . . . . . . . . . .5

CellBW
NaOH
fi
OxyChem
OxyChem is a registered trademark of Occidental Chemical Corporation.
fi
• Unloading and Handling Liquid Caustic Soda . . . .7

• Equipment for Handling Caustic Soda . . . . . . . .14

Foreword • Technical Data . . . . . . . . . . . . . . . . . . . . . . . . . . .17

This handbook outlines the methods for
handling, storing, preparing and using caustic
soda. It includes information on the manufacture, • Dilution Calculations . . . . . . . . . . . . . . . . . . . . . . .32
physical properties, safety considerations and
analytical methods for testing caustic soda.
• Methods of Analysis . . . . . . . . . . . . . . . . . . . . . . .34
Additional information and contacts can be
found at www.oxychem.com

Occidental Chemical Corporation (OxyChem)

Basic Chemicals Group
Occidental Tower
5005 LBJ Freeway
Dallas, TX 75244

"Important: The information presented herein, while not guaranteed, was prepared by technical personnel and is true and accurate to the best of our knowl-
edge. NO WARRANTY OF MERCHANTABILITY OR OF FITNESS FOR A PARTICULAR PURPOSE, OR WARRANTY OR GUARANTY OF ANY OTHER
KIND, EXPRESS OR IMPLIED, IS MADE REGARDING PERFORMANCE, SAFETY, SUITABILITY, STABILITY OR OTHERWISE. This information is not
intended to be all-inclusive as to the manner and conditions of use, handling, storage, disposal and other factors that may involve other or additional legal,
environmental, safety or performance considerations, and OxyChem assumes no liability whatsoever for the use of or reliance upon this information. While
our technical personnel will be happy to respond to questions, safe handling and use of the product remains the responsibility of the customer. No sugges-
tions for use are intended as, and nothing herein shall be construed as, a recommendation to infringe any existing patents or to violate any Federal, State,
local or foreign laws."

Occidental Chemical Corporation 2009


Caustic soda (sodium hydroxide
or NaOH) is most commonly manu-
factured by the electrolysis of a
sodium chloride (NaCl) solution.
OxyChem manufactures caustic
soda using either membrane or
diaphragm electrolytic cells.
OxyChem does not use mercury
based electrolytic cells to produce
caustic soda. The co-products
formed from the electrolytic produc-
tion of caustic soda are chlorine
and hydrogen.
The largest users of caustic soda
are the pulp and paper, detergent
and chemical industries. Caustic
soda is also used in the alumina,
oil and gas and textile industries,
mostly for its alkalinity value.
OxyChem has played a leading
role in providing caustic soda to
meet the increasing demands of
industry. OxyChem plants are
strategically located to conveniently
and economically serve industry.
Caustic soda is one of the very
few chemicals utilized in a very
broad range of applications. Some
principal products or processes in
which caustic soda is used are:
• Acid Neutralization
• Agricultural Chemicals
• Aluminum
• Battery Recycling
• Bleach
• Boiler Compounds
• Cellulose Film
• Chemicals:
Ammonia
Amyl Amines
Cresol
Ethylene Amines
Formic Acid
Glycerine
Introduction 2 of 44
Terminals are used to maintain OxyChem produces caustic soda
stocks of our caustic soda in many at the following locations:
principal cities. Distributor stocks • Battleground, TX (Diaphragm)
are also available in these and
• Convent, LA (Diaphragm)
many other cities and form a net-
work of supply for the end user’s • Geismar, LA (Membrane and
convenience. Diaphragm)
Liquid caustic soda is available as • Ingleside, TX (Diaphragm)
a 50% solution in two main grades. • Niagara Falls, NY (Diaphragm)
The name of the grades corre- • Taft, LA (Diaphragm)
sponds to the equipment used to
produced the caustic soda; mem- • Wichita, KS (Membrane and
brane grade and diaphragm grade. Diaphragm)
Specification sheets for each grade
can be found on our website at
www.oxychem.com
To be technically correct, only
molten caustic soda should be
called liquid, but since the term liq-
uid caustic soda has historically
been used to describe solutions of
caustic soda, it is used in this doc-
ument interchangeably with the
term solution.
Principal Uses and
Consumption of
Caustic Soda
Maleic Anhydride • Glass-Batch Wetting
Pentaerythritol • Ion-Exchange Resin
Phenol Regeneration
Propylene Oxide • Metal Production and Casting
Polycarbonates • Ore Flotation and Processing
Salicylic Acid • Paint Removers
Sodium Aluminate • Petroleum Refining
Sodium Hydrosulfide • pH Adjustment
Sodium Hypochlorite • Pharmaceuticals
Sodium Phosphates • Pigments
Styrene • Pool & Spa chemicals
Vinyl Chloride Monomer • Pulp & Paper
• Cleaning Formulations • Rayon
• Corn Syrup • Silicates
• Detergents • Soap
• Drain Cleaners • Surfactants
• Dyestuffs • Textile Bleaching, Dyeing, and
• Ethanol Fermentation Mercerizing
• Food Processing • Vegetable Oil Processing
• Fruit & Vegetable Peeling • Water Treatment
 Manufacturing
Process 3 of 44

Caustic soda is produced by
OxyChem by an electrolytic
process as shown below. Brine,
prepared from sodium chloride
(NaCl), is electrolyzed in either a
membrane cell or a diaphragm cell.
The production of caustic soda
(NaOH) also results in the co-prod-
ucts of chlorine and hydrogen.
In the membrane process, a
solution of approximately 30% in
strength is formed. The solution is
then sent to evaporators, which
concentrate it to a strength of 50%
by removing the appropriate
amount of water.
The diaphragm process is very
similar to the membrane process
except that a solution of only 10-
12% is formed in the cell.
Therefore, additional evaporation is
required to reach the saleable con-
centration of 50%.
The caustic soda solution is
inventoried in storage tanks prior to
shipment. The product is shipped
in tank trucks, railcars, barges and
ships.
The major difference in the two
grades is the amount of starting
material (sodium chloride) remain-
ing in the final product. Membrane
grade caustic soda will have less
than 100ppm of the sodium chlo-
ride remaining in the product.
Diaphragm grade material will have
less than 1.2% sodium chloride.
Several other differences can be
seen in the products when the
specification sheets are compared.

2NaCl + 2H2O electricity 2NaOH + Cl2 + H2

Production Flowcharts

Membrane Diaphragm

NaCl + H2O = Brine NaCl + H2O = Brine

Brine Treatment Brine Treatment

and purification

hydrogen
hydrogen

Electrolysis Electrolysis electricity

electricity
Membrane Cell Diaphragm Cell

chlorine
chlorine

Cell Liquor
30% Caustic Soda 12% Caustic Soda

NaCl
Concentration Concentration

50% Liquid Filters

Caustic Soda Storage

50% Liquid
Caustic Soda Storage
 Methods of Shipping
Liquid Caustic Soda 4 of 44

Liquid caustic soda is available

from OxyChem’s many plants and
terminals in tank truck, tank car,
barge and ship quantities. Each
form of transportation has its own
advantages. The type of service
selected will depend upon such
factors as size and location of
storage, rate of consumption,
plant location, freight rates, etc.

Caustic soda, liquid, is regulated by

the U.S. Department of
Transportation (DOT) and is classi-
fied as a corrosive material.
The DOT identification
number is UN I824 for liquid caus-
tic soda.

Caustic soda in any concentra-
tion must be respected by every-
one who handles and uses it.
Before starting to work with it,
the user should be aware of its
properties, know what safety
precautions to follow, and know
how to react in case of contact.
Accidental exposure to caustic
soda may occur under several
conditions. Potentially haz-
ardous situations include han-
dling and packaging operations,
equipment cleaning and repair,
decontamination following spills
and equipment failures.
Employees who may be subject
to such exposure must be pro-
vided with proper personal pro-
tective equipment and trained in
its use. Some general guidelines
follow.
• Read and understand the latest
Material Safety Data Sheet.
• Provide eyewash fountains and
safety showers in all areas where
caustic soda is used or handled.
Any caustic soda burn may be
serious. DO NOT use any kind of
neutralizing solution, particularly
in the eyes, without direction by a
physician.
• Move the patient to a hospital
emergency room immediately
after first aid measures are
applied.
FIRST AID MEASURES
For Eyes: If for any reason
caustic soda contacts the eyes,
flood the eyes immediately with
plenty of clean water. Continue
flushing for at least 15 minutes.
While flushing, forcibly hold the
eyelids apart to ensure rinsing of
the entire eye surface. Do not use
any kind of neutralizing solution
in the eyes.
GET MEDICAL ATTENTION
IMMEDIATELY.
Safety in Handling
Caustic Soda 5 of 44
For skin: If caustic soda comes
in contact with skin or clothing,
flush with plenty of clean water for
at least 15 minutes. Remove conta-
minated clothing and footwear.
CHEMICAL FACE
Thoroughly wash affected clothing SPLASH SHIELD
and rubber/vinyl footwear. Discard GOGGLES
contaminated leather footwear.
GET MEDICAL ATTENTION
IMMEDIATELY.
For inhalation: If a worker is
overcome due to the inhalation of
caustic soda dust, mist or spray,
remove them from the contaminat-
ed area to fresh air. If breathing is
difficult, have a trained person
administer oxygen. If breathing has
stopped, have a trained person CHEMICAL
administer artificial respiration.
SUIT
GET MEDICAL ATTENTION RUBBER
IMMEDIATELY. GLOVES
For ingestion: Although it
is unlikely in an industrial
situation that caustic soda would
be ingested, it could be swallowed
accidentally. If that occurs, DO
NOT induce vomiting. Give large
quantities of water. If vomiting
occurs spontaneously, position indi- RUBBER
BOOTS
vidual’s head to keep airway clear.
NEVER give anything by mouth to
an unconscious
person. GET MEDICAL ATTEN-
TION IMMEDIATELY. • The use of a face shield may be
appropriate when splashing can
PROTECTIVE EQUIPMENT occur, including loading and
OSHA requires employers to unloading operations.
supply suitable protective equip- • Wear rubber gloves or gloves
ment for employees. When han- coated with rubber, synthetic
dling caustic soda, the following elastomers, PVC, or other plas-
protective equipment is recom- tics to protect the hands while
mended: handling caustic soda. Gloves
• Wear suitable chemical splash should be long enough to come
goggles for eye protection dur- well above the wrist. Sleeves
ing the handling of caustic should be positioned over the
soda in any concentration. The glove wrists.
goggles should be close-fitting • Caustic soda causes leather to
and provide adequate ventilation disintegrate quite rapidly. For this
to prevent fogging, without allow- reason, wear rubber boots. Wear
ing entry of liquids. the bottoms of trouser legs out-
 Safety in Handling
Caustic Soda 6 of 44

side the boots. DO NOT tuck in. • When making solutions, always HANDLING LIQUID
• Wear chemical resistant clothing add the caustic soda slowly to CAUSTIC SODA
for protection of the body. the surface of the water with con- In handling caustic soda solu-
Impregnated vinyl or rubber suits stant agitation. Never add the tions, care must be taken to avoid
are recommended. water to the caustic soda. solidification which will plug
• Wear hard hats for some protec- Always start with lukewarm water pipelines and equipment. Graph 1
tion of the head, face and neck. (80 -100°F). Never start with hot (pg. 29) shows the freezing points
• If exposures are expected to or cold water. Dangerous boiling for solutions of caustic soda at vari-
exceed accepted regulatory limits or splattering can occur if caustic ous concentrations.
or if respiratory discomfort is soda is added too rapidly, Should a caustic soda solution
experienced use a NIOSH allowed to concentrate in one become frozen in process equip-
approved air purifying respirator area or added to hot or cold liq- ment or piping, care must be taken
with high efficiency dust and mist uids. Care must be taken to when thawing the material. Use
filters. avoid these situations. only low pressure (10 PSIG or
• In case of a spill or leak, stop the less) steam. Accelerated corrosion
PROTECTIVE PRACTICES leak as soon as possible. After can occur in areas where equip-
• Avoid breathing dust, mist or containment, collect the spilled ment is subjected to extremely high
spray of caustic soda. material and transfer to a chemi- temperatures.
• Wear proper protective equip- cal waste area. Remove large liq-
ment. If warranted, wear uid spills by vacuum truck.
approved respiratory protection. Neutralize residue with dilute
• Keep equipment clean by wash- acid. Flush spill area with water
ing off any accumulation of caus- and follow with a liberal covering
tic soda. of sodium bicarbonate or other
• Weld pipelines where practical. acceptable drying agent.
Use flanged joints with gaskets
made of caustic soda resistant
material such as rubber, PTFE,
or EPDM rubber. If a screwed fit-
ting is used, apply Teflon® tape to
the threads.
• When disconnecting equipment
for repairs, first verify that there
is no internal pressure on the
equipment and that the equip-
ment has been drained and
washed.
• Provide storage tanks with suit-
able overflow pipes. Overflow
pipes should be directed near the
bottom of the diked area.
• Shield the packing glands of
pumps to prevent spraying of
caustic solutions in the event of a
leak.
• When releasing air pressure from
a pressurized system, take every
precaution to avoid spurts or
sprays of caustic solution.

GENERAL INFORMATION
Caustic soda in liquid form
has a markedly corrosive action
on all body tissue. Even dilute
solutions may have a destructive
effect on tissue after prolonged
contact. Inhalation of concentrat-
ed mists can cause damage to
the upper respiratory tract, while
ingestion of liquid caustic soda
can cause severe damage to the
mucous membranes or other tis-
sues where contact is made. In
addition, considerable heat is
generated when liquid caustic
soda is mixed with water which
can result in boiling or splatter-
ing. When diluting, always add
caustic soda to water; never add
water to caustic soda.
It is important that those who
handle caustic soda are aware of
its highly reactive and corrosive
properties and know what pre-
cautions to take. In case of acci-
dental exposure, immediately
flush exposed area with large
amounts of water and seek med-
ical attention. For more specific
information refer to the Safety in
Handling Caustic Soda section
of this handbook and to the
MSDS.
PLACEMENT OF THE CAR FOR
UNLOADING
1. After the car is properly spot-
ted, DOT regulations require
that the hand brake be set and
the wheels blocked before any
connections are made.
2. Caution signs must be placed
at both ends of the car being
unloaded to warn people and
switching crews approaching
the car. DOT regulations state
that caution signs must be
placed on the track or car to
give warning to persons
approaching the car from the
open end or ends of siding.
Caution signs must be left up
Unloading and Handling Liquid
Caustic Soda in Tank Cars
until the car is unloaded and
disconnected from the dis-
charge connections. Signs
must be made of metal or other
suitable material, at least 12x15
inches in size, and bear the
words, “STOP-TANK CAR
CONNECTED”, or “STOP-MEN
AT WORK.”
3. It is recommended that derail
attachments be placed at the
open end or ends of siding,
approximately one car length
away.
4. Before hooking up a car, the
responsible individual should
first locate and test the nearest
eyewash and safety shower.
Purge water through each to
remove rust that may have
accumulated.
UNLOADING PRECAUTIONS
1. Only responsible and well
supervised employees should
be entrusted with the unloading
of liquid caustic soda.
Unloading operations must be
monitored while the car is con-
nected.
2. Since serious burns can result
from contact of caustic soda
with the skin and eyes, workers
should be well protected and
cautioned to exercise care.
Persons hooking up a car
should wear the following per-
sonal protective equipment:
• Hard hat
• Chemical splash goggles
• Face shield
• Rubber, steel-toed boots
• Rubber gloves or
equivalent
• Vinyl or rubber jacket and
pants
• If warranted, wear approved
respiratory protection
7 of 44
3. A car of caustic soda should be
unloaded only when adequate
lighting is available throughout
the entire unloading process.
4. Before starting to unload, make
certain that the tank car is vent-
ed and that the storage tank is
vented and has sufficient
capacity.
5. No one should enter the car
under any circumstances.
6. If a tank car needs to be moved
when partially unloaded, DOT
regulations require that all
unloading lines must be discon-
nected and car closures must
be replaced.
7. A suggested method for sam-
pling is to draw intermittent
samples from a 1/2” sample
line, connected to a vertical
section of the unloading line.
The sample line should be fitted
with a valve and a 1/4” nipple.
8. OxyChem’s liquid caustic soda
is shipped in well insulated and
specially lined tank cars. Linings
in these tank cars will withstand
temperatures up to 225°F.
Recommended steam pressure
used to heat up a rail car is lim-
ited to 10psig max due to this
fact. To prevent damage to the
linings, neither water nor steam
should be added directly into
the tank cars if the car contains
a level of caustic.
9. Unloading lines should be cov-
ered with suitable insulation and
heated just prior to transfer of
liquid caustic soda to storage.
The preferred method of heat-
ing is to provide electric or
steam heat tracing around the
unloading line, under the insula-
tion. An alternate method is to
provide tees in the unloading
line so that steam (or hot water)
can be run through the unload-
ing line just prior to its use.

These precautions will prevent
the solidification of liquid caus-
tic soda in cold unloading lines.
Running steam through
unloading lines will increase
corrosion in unlined steel
piping systems and iron
pickup in the product.
10. If compressed air is used in
unloading operations, it is
important that all fittings be
inspected for leaks or other
defects before unloading.
Dome fittings in particular
should be inspected. If leaks
are found, unloading operations
should be suspended until they
are corrected.
11. General purpose caustic rail
car tanks are structurally
designed and constructed for
100 psig, and have a design
burst rating of 500 psig. Per 49
CFR 179 and the AAR
Specifications for Tank Cars, a
pressure relief device is
installed sized for a fire sce-
nario, that is set for 75 to 165
psig. The higher set pressure is
allowed due to the premature
failure of the lower rated relief
devices that occurred during
transport handling, and resulted
in injuries to rail road person-
nel. Even through they are
designed and equipped as
such, these are NOT pressure
rail cars, nor should they be
padded above what OxyChem
and the Chlorine Institute rec-
ommends (20-25 psig).
After a rail car is loaded with
product, it is leak checked at
approx 30 psig to meet the
DOT shipping requirement, and
that test pressure is released
prior to shipping.
Because of inherent shaking
and jarring experienced by the
rail car and contents during the
shipping process, gaskets and
joints can loosen up and cus-
tomers should be cautious of
that possibility. If pressure
Unloading and Handling Liquid
Caustic Soda in Tank Cars 8 of 44
unloading, particular areas to outlet, which should be opened
watch are the manway gasket, sufficiently to relieve conden-
the bottom flange gasket (when sate and direct it toward the
bottom unloading), and the top ground or into a sewer. As con-
operator gland area for bottom tents liquefy, the valve may be
outlet valve (if so equipped). closed further to conserve
Additionally the top operated steam.
bottom outlet valve reach rods 5. If necessary, steam can be con-
can in rare instances, come nected to the rail car steam
detached during transit, and coils. A condensate return line,
there have been reports that pressure reducing valve, and/or
these rods can be 'pushed up' steam trap should be used. Do
from a rail car if unloading not exceed a steam pressure of
pressures > 30 psig are used. 10 psig. Using steam pressure
above 10 psig may damage the
HANDLING IN COLD WEATHER railcar lining.
6. The amount of material that is
Since OxyChem tank cars
frozen in a caustic soda rail car
are well insulated and liquid caustic
is dependent upon the outside
soda is loaded hot, it usually
temperature, wind chill, and the
arrives at its destination in a liquid
time between when the rail car
condition. However, since 50% liq-
is loaded and unloaded.
uid caustic soda begins to crystal-
Although it is unlikely, it is pos-
lize at 54°F, in cases of unusual
sible for a caustic soda rail car
delays in transit, freezing may take
to be totally frozen. If the caus-
place in cold weather. If freezing
tic soda in a rail car is totally
has occurred, the following proce-
frozen, it may be necessary to
dure should be used.
apply steam to the rail car jack-
1. Carefully open tank car dome
et for two days (48 hours) to liq-
cover.
uefy all of its contents.
2. If a layer of caustic soda has
7. When examination indicates
formed over the contents of the
that the contents have liquefied
car, this crust should be broken
and operation of the valve rod
before admitting steam to the
shows that the bottom dis-
jacket around the bottom dis-
charge valve is free, the caustic
charge valve. The puncturing of
soda is ready for unloading.
the crust permits expansion of
the liquid as it increases in tem-
The unloading temperature of
perature.
50% caustic soda should be
3. If no crust is present, determine
less than 120oF to minimize
if crystals have formed on the
corrosion of unlined steel
bottom of the car by probing the
piping systems and equip-
bottom with a rubber-capped
ment.
8. If the above measures do not
rod introduced through the
liquefy the contents on the car,
dome opening.
contact your OxyChem repre-
4. If freezing has occurred, con-
sentative.
nect a steam line (10 psig or
less) to the jacket around the
bottom discharge valve.
Connect a condensate return
line at the valve jacket steam
outlet. If a condensate return
line is not used, it is advisable
to connect a valve at the steam
 Rail Car Drawing
Details of Caustic Soda Car 9 of 44

Figure 1
6. Protective Housing Cover

5. 2" Unloading
Safety Chain & Toggle Connection

21. Plug Cock

1. Stuffing Box Cover 7. 1" Air Connection

Valve
4. Manway Cover
Safety Guard
18. Outlet Valve Operating Rod
Stuffing Box 2. Manway 3. Safety Top Unloading
Vent Assembly
19. 4" Insulation 8. 2" Eduction Pipe

20. 1/8" Steel Shell

7/16" Steel Tank

Handbrake
Placard
Warning
Signs

10. Steam Coil

Inlet & Outlet

Electrical Ground Eduction Pipe

18. Outlet Valve Bottom Unloading
Operating Rod Assembly Assembly

11. Bottom Outlet 17. Heating Coils

Valve 8. 2" Induction Pipe

12. Steam Chamber

9. Pipe Guide
16. Steam Outlet 13. Steam Inlet

7/16" Steel Tank

19. 4" Insulation 20. 1/8" Steel Shell

14. Supplementary Valve

15. Plug in Bottom Outlet

 Unloading Liquid Caustic Soda
in Tank Cars 10 of 44

Rail cars can be either bottom
unloaded (gravity, pump or pressure)
or top unloaded (with air pressure).
Refer to appropriate unloading proce-
dure based on the method to be
employed.
UNLOADING THROUGH
BOTTOM OUTLET VALVE
1. Open the dome cover and deter-
mine if the contents of the car
are liquid. If not, see “Handling
in Cold Weather.” Keep the
dome cover at least partially
open during the entire unloading
operation to vent the tank car.
2. Refer to Figure 1. Insure that the
bottom outlet valve is closed
tightly. The valve rod which oper-
ates the bottom discharge valve
has a handle on it which is locat-
ed outside the dome of the car.
The handle can be reversed and
serves as a cap in transit.
3. Remove the pipe plug, then care-
fully open the supplementary
valve to drain any liquid that may
have seeped past the bottom
outlet valve during transit. If the
supplementary valve cannot be
opened, the application of steam
from a steam lance, directed on
the valve, should free it for open-
ing.
4. Attach the unloading line to the
bottom of the supplementary
valve.
5. Check the unloading line to see
that all valves are in the proper
position for unloading.
6. Open the bottom outlet valve by
turning the valve rod to allow
contents to flow by gravity to
pump or tank. If the bottom outlet
valve does not open upon appli-
cation of light pressure, frozen
caustic soda is probably present
in the bottom of the car.
Application of steam to the heat
coils may be necessary. See
“Handling in Cold Weather.”
7. Compressed air can be used to
increase the flow rate of caustic
soda to storage or to transfer liq-
uid without the use of a pump. If
compressed air is to be used,
check the rupture disk in the
dome to be sure it is intact.
Close the dome cover securely.
Remove the one-inch air inlet
plug and connect a flexible air
line at this point. The air line
should have a release valve, oil
trap, pressure relief valve set at
20 PSIG, pressure reducing
valve set at 18 PSIG and a shut-
off valve. Apply air pressure to
the car slowly. Note that the
pressure relief device (rupture
disk and/or pressure relief valve)
in the dome will relieve at a pres-
sure between 75 PSIG and 165
PSIG, depending on the type of
car. Refer to the stenciling on the
side of the railcar.
8. When the car and unloading line
are empty, shut off air supply and
open the release valve.
9. When the tank car is empty and
the discharge pipe has complete-
ly drained, disconnect the air
line, if used, close the bottom
outlet valve and supplementary
valve, and detach the unloading
line at the car.
10. Prepare the car for return.

Figure 2: Bottom Unloading

To process

Tank inlet valve

Vent

STORAGE TANK

TANK CAR

Steam coils

Steam jacket

2” Steel pipe Drain

Union
Pump

Rail car Low line drain valve

unloading valve
Pump inlet valve
 Unloading Liquid Caustic Soda
in Tank Cars 11 of 44

UNLOADING THROUGH
DOME WITH AIR PRESSURE
1. Open the dome cover to deter-
mine if the contents of the car
are liquid. If not, see “Handling in
Cold Weather.”
2. Close the dome cover and fasten
securely, making certain that it is
air tight. Check that the rupture
disk in the dome is intact.
3. Check that the product storage
tank is vented and has sufficient
capacity.
4. After opening the protective
housing cover, connect the
unloading line to the two-inch top
unloading valve. After removing
the protective housing cover, a
flexible steel hose connection for
the unloading line is recommend-
ed since a car may rise as much
as 2” during unloading.
5. Connect the flexible air supply
line to the one-inch air inlet
valve. This line should have a
release valve, oil trap, pressure
relief valve set at 20 PSIG, pres-
sure reducing valve set at 18
PSIG and a shut-off valve. Note
that the relief device (rupture disk
or pressure relief valve) in the
dome will relieve at a pressure
between 75 and 165 PSIG,
depending on the type of car.
Refer to the stenciling on the
side of the railcar.
6. Apply air pressure slowly until
there is a normal flow of liquid to
the storage tank. The pressure
should be adjusted and main-
tained until the tank car is com-
pletely empty. A drop in air pres-
sure or the sound of air rushing
through the unloading line indi-
cates that the tank car is empty.
7. Shut off the air supply, open the
release valve, and allow the
eduction pipe to drain.
8. When the eduction pipe has
drained and the tank car is at
atmospheric pressure, discon-
nect the air supply line at the car.
9. Do not enter the car to make an
inspection.
10. Open the dome cover and deter-
mine if the car is empty. If empty,
disconnect the unloading line at
the car, replace pipe plugs and
tightly replace the dome cover
and the protective housing cover.
11. Care should be taken not to spill
caustic soda on the car, since it
will cause damage to the car and
may endanger workers handling
the empty car on its return.
12. Prepare the car for return.
PREPARING EMPTY TANK
CARS FOR RETURN
1. Make sure the bottom outlet
valve and supplementary valve
are closed.
2. Disconnect the unloading line
and replace the bottom outlet
plug. Do not replace closures on
steam openings.
3. Close dome cover and fasten
securely.
4. Return the empty tank car
promptly in accordance with the
shipper’s instructions. The ship-
per’s routing directions must be
followed in all instances.

Figure 3: Top Unloading Relief valve

set at 20 psig
Tank inlet valve
Shut-off Compressed
valve air inlet
Flexible connections
2” Steel pipe Release valve Pressure reducing
valve set to 18 psig
1” Steel pipe Pressure gauge

Vent

STORAGE TANK
Eduction
Pipe
TANK
CAR

Steam coils

To
process
Drain

CARRIER RESPONSIBILITIES
OxyChem tank truck drivers have
received instructions regarding
equipment and delivery proce-
dures. If an OxyChem arranged
carrier, delivering caustic soda to
your plant, fails to adhere to the fol-
lowing guidelines, please contact
OxyChem so that corrective action
can be taken.
Equipment
Equipment must meet
Department of Transportation regu-
lations, Code of Federal
Regulations (CFR), Title 49.
Tank Truck Specification
Tank trucks should meet the
established DOT requirements for
hauling liquid caustic soda.
Four DOT “CORROSIVE” plac-
ards must be permanently affixed
to the cargo tank.
Unloading Equipment
If unloading is by gravity to stor-
age or customer’s unloading pump,
no special equipment is needed.
If unloading is by truck-mounted
pump, use only an all iron or nickel
unit. The pump can be driven by a
tractor powered take-off or an aux-
iliary gasoline engine. Use at least
a 2-inch pump line.
If unloading is by compressed
air, the tank vessel must meet the
DOT requirements of the CFR, Title
49. The line used to supply air to
the tank truck is required to be
equipped with: pressure reducing
valve, pressure release valve,
pressure gauge, pressure reducing
valve and pressure relief valve.
The relief valve should be set at a
maximum pressure of 20 PSIG and
the pressure reducing valve should
be set at 2 to 3 pounds lower.
Whether this equipment is attached
permanently to the tank or carried
as an assembled unit to be
attached at each unloading, it
should be properly maintained and
periodically tested.
Unloading Liquid Caustic Soda
in Tank Trucks
A 40 foot length of air hose is
required if the customer’s air sup-
ply is used. When compressed air
is not available from the customer’s
plant, trucks equipped with pumps
or air compressors can be provided
at the customer’s request.
Unloading Lines
Unloading hoses must be con-
structed of material resistant to
caustic soda. Hoses should be at
least 2 inches in diameter and 15
to 30 feet in length.
Whether the unloading hose is
fitted with a union, pipe flange, or a
quick type coupler, the truck driver
should have available matching fit-
tings and tools to facilitate a con-
nection to a 2-inch or 3-inch
threaded pipe.
TRUCK DRIVER
RESPONSIBILITIES
Truck drivers must obtain permis-
sion to unload from the proper
authorities and observe any special
instructions from the customer.
Truck drivers must wear the pro-
tective equipment required by
OxyChem as listed under
Protective Equipment, (pg. 6) or by
customer, whichever is more inclu-
sive, and at all times follow safe
handling practices. Customers
must not allow truck drivers who do
not meet these requirements to
unload.
12 of 44
The following unloading
procedures are recommended:
• Check the operation of the safety
shower and eyewash fountain.
Purge water through each to
remove rust that may have accu-
mulated.
• If a shower and eyewash are not
available, a water hose connect-
ed to a source of water is
required. If the valve on the line
is not conveniently located near
the unloading area, leave a
stream of water flowing during
unloading.
• Connect one end of the unload-
ing hose to the customer’s stor-
age tank fill line.
• During cold weather and if facili-
ties are provided, preheat with
steam the fill line, the unloading
hose, and, if needed, the truck
outlet.
• Check the unloading line to be
sure that it is open.
• Connect the unloading hose to
the discharge outlet on the tank
truck.
• Start the pump or start pressuriz-
ing the tank, depending on the
type of equipment used.
• Open the valves on the truck
discharge line.
• Stand by until the truck cargo is
completely unloaded.
• If compressed air is used,allow
the air to flush out the lines to the
storage tank and then cut off the
air supply.
• When a pump is used, flush out
the unloading line before discon-
necting the hose. If water is
available, a small quantity can
be added into the truck while the
pump is running to flush out the
line. Air or water can be used to
flush the caustic soda in the line
into the storage tank or back to
the truck. If no water is available
for flushing out lines, exercise
great caution when lines are dis-
connected.

• Close the valve on the storage
fill line.
• Close all valves on the tank
truck.
• In some installations the cus-
tomer’s fill line is fitted with a
drain to be used instead of flush-
ing the line before the hose is
disconnected.
• Disconnect the hose with caution
and discharge any caustic soda
remaining in the hose to a suit-
able container.
• Unload caustic soda in an area
with adequate safeguards for
spill control. No caustic soda
should be spilled, but in the
event a small amount is spilled,
hose down the area with water.
Clean up all spills and dispose in
accordance with federal, state
and local regulations.
Unloading Liquid Caustic Soda
in Tank Trucks 13 of 44
FACILITY EQUIPMENT
Typical installations of storage
vessels for receipt of truck ship-
ments are similar to those shown in
Figures 2 and 3 for rail car deliver-
ies.
A storage tank with a minimum
capacity of 1.5 tank cars is recom-
mended.
A fill line to the top of the storage
is strongly recommended. If a bot-
tom fill line is used, the truck driver
must be informed.
A permanent fill line in close
proximity to the tank truck unload-
ing area is required.
A 2-inch or larger fill line is rec-
ommended.
A 3/4-inch valve connection is
recommended on the fill line for
use in flushing out the line with air,
water, or steam. It can be used as
a drain.
Cap or close the end of the fill
line when not in use.
A source of running water for use
during unloading operations is
required. A safety shower and eye-
wash fountain are recommended.

GENERAL CONSIDERATIONS
Caustic soda is a corrosive
chemical which is normally handled
in either steel, nickel, nickel alloys
or certain types of plastic equip-
ment. The specific material will
depend on the conditions under
which the material is being used.
Temperature, solution concentra-
tion, location and safety considera-
tions are all important factors in
equipment selection.
MATERIALS OF CONSTRUCTION
The most common construction
materials for handling and storing
caustic soda solutions are black
iron and mild steel; however, liquid
caustic soda will attack these met-
als at elevated temperatures. The
ideal storage temperature for caus-
tic soda solutions is 80 to 100°F. In
steel systems, temperatures above
120°F will cause accelerated corro-
sion and iron contamination of the
caustic (above 120°F, cracking can
occur if concentrated caustic is
processed in steel equipment that
has not been stress relieved.)
Where iron contamination or corro-
sion is unacceptable, epoxy lined
steel, 316L and 304L stainless
steels are recommended. 316L
and 304L stainless is acceptable to
200°F. At temperatures above
200°F, nickel is typically used but
Monel®, Inconel®, or Hastelloy®
can also be used. Consult with the
epoxy supplier about the working
temperature range of a particular
epoxy lining.
Plastics, such as polyethylene,
polypropylene, PVC, and CPVC,
are chemically suitable with caustic
soda. They can be used to prevent
iron contamination if maximum
temperatures for each material are
not exceeded. The manufacturer of
the tank, drum, piping or equipment
in question should be contacted to
Equipment For Handling
Caustic Soda
determine the exact limitations of
the specific plastic. Aluminum, cop-
per, zinc, lead and their alloys
(e.g., brass and bronze) are NOT
suitable. Caustic soda readily
attacks these materials.
STORAGE TANKS
Tanks can be either vertical or
horizontal. They are usually fabri-
cated from at least 1/4-inch steel
plate. A 1/8-inch corrosion
allowance should be included in
the design. If iron contamination is
a problem, tanks can be fabricated
from 304L or 316L stainless steel.
If the tanks are large, it’s usually
more economical to fabricate a
steel tank and line it with an epoxy
coating. Plastic tanks are usually
fabricated from polypropylene or
FRP (Since caustic can attack
glass reinforcement fibers of
improperly constructed FRP tanks,
care must be taken to ensure that
the FRP tanks are built with the
proper reinforcing materials, resins,
catalysts, curing procedures and
corrosion barriers).
The product draw-off line should
be at least 4 inches above the bot-
tom of the tank and the drain con-
nection should be at the lowest
point in the tank. This will facilitate
drainage during periodic cleaning
of the tank. Most tanks have a level
transmitter for measuring liquid
level.
Where heating is required, an
external heat exchanger with a cir-
culating pump or internal steam
heating coils are most commonly
employed. The preferred materials
for the coils are nickel, Monel®, or
Inconel®. Despite this, stainless
steel is most commonly used
because of cost considerations.(At
14 of 44
high temperatures, stainless steel
may crack). If it is necessary to
insulate the storage tank, a two-
inch layer of polyurethane foam or
cellular glass should be adequate.
Proper design of a storage sys-
tem will include adequate contain-
ment in case of tank failure. State
and local regulatory authorities
should always be consulted during
the design phase of construction.
TANK CLEANING AND
PASSIVATION
Tank cleaning is dependent on
the product stored in it previously.
A tank that previously contained
caustic soda requires scale
removal, wall thickness testing,
rinsing, passivation, floor cleaning,
and immediate filling. A tank previ-
ously containing another product
requires cleaning with an appropri-
ate solvent or soap, as well as the
other steps mentioned above.
Scale removal is accomplished
by blasting the walls with an abra-
sive such as sand or pecan shells.
Abrasives containing high percent-
ages of metals are not recom-
mended.
The wall thickness of the tank
should be measured to ensure that
the tank has structural integrity for
the density of the product and the
height of product in the tank.
Passivation requires permeation
of the steel tank walls with caustic
soda. This is usually accomplished
by spraying the cleaned walls with
a hot solution of caustic soda.
Temperatures of 100 - 140°F and
solutions of 5 - 20% are recom-
mended. While this is more of an
art than a science, a standard rec-

ommendation would be spraying
the walls for 2-4 hours with 10%
solution at 140°F. The larger the
tank the longer it should be
sprayed to complete the passiva-
tion. Utilizing a hotter and stronger
solutions will require less time for
passivation. One way to achieve
the solution heat necessary is to
dilute 50% caustic soda to 20%.
The heat of dilution will cause the
caustic soda temperature to rise.
Additional heat may be necessary
to achieve optimal solution temper-
atures. The coating of the tank
walls is best accomplished with an
elliptical sprayer. If this type of
sprayer is not available, the spray-
ing may be done manually with
extreme caution taken to protect
the operator.
After passivation, the tank bottom
must be cleaned out as well as
possible. The quality of the initial
product stored in the tank will
depend greatly upon the extent to
which the tank bottom is cleaned of
scale abrasive compound. If an
elliptical sprayer is used for the
cleaning, a squeegee will need to
be used to clean the tank bottom. If
manual spraying is used for clean-
ing, the sprayer can be used to
push the scale and abrasive toward
the sump followed up by use of a
Equipment For Handling
Caustic Soda
squeegee.
After cleaning, the tank should be
filled with caustic soda as soon as
possible. This will prevent the tank
walls from losing their passivation.
If the tank cleaning is not complete-
ly successful, it may be necessary
to filter the initial product from the
tank to keep it free from particulate
matter. This would require a 5-10
micron filter media housed in a unit
that would be acceptable with the
temperature, pressure, and chemi-
cal.
PIPING AND VALVES
Pipelines are usually at least two
inches in diameter and constructed
of Schedule 40 black iron or mild
steel with welded or flanged joints.
Where disconnects are necessary,
flanged joints are preferred to facili-
tate maintenance. A safety shield of
wrap-around polypropylene is rec-
ommended for all flanged joints.
This will protect against spraying in
case a gasket leaks.
Proper pipeline design includes
an adequate pitch to permit com-
plete draining. Avoid any loops or
pockets. Lines should also include
water or air connections for purging
after use.
Where slight iron contamination
is unacceptable, CPVC, polypropy-
lene, polypropylene-lined steel, and
Teflon® lined steel pipe are suit-
able materials. Pay special atten-
tion to suitable operating tempera-
15 of 44
tures and pressures with these
materials.
Ductile iron, cast steel, stainless
steel, Alloy 20, and Teflon®-lined
quarter-turn plug or ball valves are
recommended for caustic soda ser-
vice. Various other types of valves
can also be used; however, keep in
mind that less elaborate fittings
provide better reliability in this ser-
vice.
PUMPS
Centrifugal pump of stainless
steel or Alloy 20 construction, with
either double mechanical seals or a
deep packing gland, is recom-
mended. Packing material should
be Teflon® impregnated, caustic
resistant fibers, or equivalent. To
avoid seals altogether, magnetically
coupled pumps could be used.
Pump location should receive
careful consideration. For ease of
operation, keep the suction lines as
short as possible. A recirculating
line will help prevent excess wear
on the pump and, in many cases,
can assist in controlling flow rates.
METERS
Caustic soda solutions can be
metered through standard rotame-
ters having non-glass tubes and
nickel or stainless steel floats.
Magnetic, coriolis or orifice-type
meters are preferred for strong, hot
solutions. They should be made of
corrosion resistant materials such
as stainless steel, alloy 20, monel
or nickel.
 Installation of Tanks 16 of 44

Figure 6: Typical Storage Tank Installation

High Level
Alarm 2” Fill Line
Level Indicator SCH 40 Pipe
24” Manway
Vent

Threaded End
Cap for
Float Tank Truck
Connections
Float Gauge
Temperature
Controlled
Steam Valve Thermowell

Inlet Outlet Valve

Outlet
Steam Trap 2” Line to Pump
Drain SCH 40 Pipe
Saddle Tank Heating Coil

*NOTE: All tanks should be located within a diked area.

High Level
Alarm 2” Fill Line
Vent Level Indicator SCH 40 Pipe
24” Manway

Float

Float Gauge Threaded End

Cap for
Tank Truck
Connections
Thermowell

Temperature
Controlled
Steam Valve
Tank Heating Coil Outlet Valve
Inlet
Outlet
Steam Trap
Drain
Reinforced Concrete Support
 Technical
Data 17 of 44
3

Table 1 Density and Caustic Soda Content of Rayon/Membrane Grade

Caustic Soda Solutions at 60°F

DEGREES TOTAL WT TOTAL WT

WT% % SPECIFIC BAUMÉ NaOH NaOH SOLUTION NaOH SOLUTION
NaOH Na2O GRAVITY [AM STD] G/L LB/GAL LB/GAL LB/CU FT LB/CU FT
1.0 0.775 1.0120 1.706 10.118 0.084 8.437 0.631 63.113
2.0 1.550 1.0230 3.259 20.457 0.171 8.529 1.277 63.804
3.0 2.325 1.0342 4.782 31.019 0.259 8.622 1.935 64.497
4.0 3.100 1.0453 6.274 41.803 0.349 8.715 2.608 65.191
5.0 3.874 1.0564 7.736 52.811 0.440 8.807 3.295 65.885
6.0 4.649 1.0676 9.170 64.042 0.534 8.900 3.995 66.581
7.0 5.424 1.0787 10.580 75.496 0.630 8.993 4.710 67.277
8.0 6.199 1.0899 11.960 87.174 0.727 9.087 5.438 67.973
9.0 6.974 1.1010 13.310 99.076 0.826 9.180 6.181 68.670
10.0 7.748 1.1122 14.630 111.210 0.927 9.273 6.937 69.367
11.0 8.523 1.1234 15.930 123.550 1.031 9.366 7.707 70.063
12.0 9.298 1.1345 17.200 136.130 1.136 9.459 8.492 70.759
13.0 10.080 1.1457 18.440 148.920 1.242 9.552 9.290 71.455
14.0 10.850 1.1569 19.660 161.930 1.351 9.645 10.110 72.150
15.0 11.630 1.1680 20.850 175.170 1.461 9.738 10.930 72.845
16.0 12.400 1.1791 22.030 188.630 1.573 9.830 11.770 73.539
17.0 13.180 1.1902 23.170 202.300 1.687 9.923 12.620 74.231
18.0 13.950 1.2013 24.300 216.200 1.803 10.020 13.490 74.922
19.0 14.730 1.2124 25.400 230.310 1.921 10.110 14.370 75.612
20.0 15.500 1.2234 26.480 244.640 2.040 10.200 15.260 76.300
21.0 16.280 1.2344 27.530 259.180 2.162 10.300 16.170 76.987
22.0 17.050 1.2454 28.570 273.940 2.285 10.390 17.090 77.672
23.0 17.830 1.2563 29.590 288.910 2.409 10.480 18.030 78.355
24.0 18.600 1.2672 30.580 304.090 2.536 10.570 18.970 79.035
25.0 19.370 1.2781 31.550 319.470 2.664 10.660 19.930 79.713
26.0 20.150 1.2889 32.510 335.070 2.794 10.750 20.910 80.389
27.0 20.920 1.2997 33.440 350.870 2.926 10.840 21.890 81.062
28.0 21.700 1.3105 34.350 366.870 3.060 10.930 22.890 81.731
29.0 22.470 1.3212 35.250 383.070 3.195 11.020 23.900 82.398
30.0 23.250 1.3317 36.120 399.450 3.331 11.110 24.920 83.057
31.0 24.020 1.3424 36.980 416.070 3.470 11.200 25.960 83.722
32.0 24.800 1.3529 37.830 432.860 3.610 11.280 27.010 84.379
33.0 25.570 1.3634 38.650 449.850 3.751 11.370 28.070 85.033
34.0 26.350 1.3738 39.450 467.010 3.895 11.460 29.140 85.681
35.0 27.120 1.3842 40.240 484.370 4.039 11.540 30.220 86.327
36.0 27.900 1.3944 41.020 501.910 4.186 11.630 31.310 86.968
37.0 28.670 1.4046 41.770 519.630 4.333 11.720 32.420 87.605
38.0 29.450 1.4148 42.510 537.520 4.482 11.800 33.530 88.237
39.0 30.220 1.4248 43.230 555.590 4,633 11.880 34.660 88.864
40.0 31.000 1.4348 43.940 573.830 4.785 11.970 35.800 89.487
41.0 31.770 1.4447 44.640 592.240 4.939 12.050 36.950 90.105
42.0 32.550 1.4545 45.310 610.810 5.094 12.130 38.110 90.717
43.0 33.320 1.4643 45.980 629.530 5.250 12.210 39.270 91.324
44.0 34.100 1.4739 46.630 648.420 5.407 12.290 40.450 91.926
45.0 34.870 1.4835 47.260 667.450 5.566 12.370 41.640 92.522
46.0 35.650 1.4930 47.880 686.640 5.726 12.450 42.840 93.113
47.0 36.420 1.5023 48.480 705.970 5.887 12.530 44.040 93.697
48.0 37.200 1.5116 49.080 725.440 6.049 12.610 45.260 94.275
49.0 37.970 1.5208 49.650 745.040 6.213 12.680 46.480 94.847
50.0 38.740 1.5298 50.220 764.780 6.377 12.760 47.710 95.412
51.0 39.520 1.5388 50.770 784.640 6.543 12.830 48.950 95.971
52.0 40.290 1.5476 51.310 804.630 6.710 12.910 50.200 96.523
 Technical
Data 18 of 44

Table 2 Density and Caustic Soda Content of Diaphragm Grade

Caustic Soda Solutions at 60°F

DEGREES TOTAL WT TOTAL WT

WT% % % SPECIFIC BAUMÉ NaOH NaOH SOLUTION SOLUTION
NaOH Na2O NaCl GRAVITY [AM STD] G/L LB/GAL LB/GAL LB/CU FT LB/CU FT
1.0 0.775 0.020 1.0121 1.726 10.120 0.084 8.438 0.631 63.122
2.0 1.550 0.040 1.0233 3.300 20.463 0.171 8.532 1.277 63.823
3.0 2.325 0.060 1.0346 4.842 31.032 0.259 8.626 1.936 64.525
4.0 3.100 0.080 1.0459 6.351 41.827 0.349 8.719 2.610 65.227
5.0 3.874 0.100 1.0571 7.829 52.846 0.441 8.813 3.297 65.930
6.0 4.649 0.120 1.0684 9.282 64.095 0.535 8.908 3.999 66.636
7.0 5.424 0.140 1.0797 10.710 75.568 0.630 9.002 4.714 67.341
8.0 6.199 0.160 1.0911 12.100 87.269 0.728 9.096 5.444 68.047
9.0 6.974 0.180 1.1024 13.460 99.195 0.827 9.191 6.188 68.752
10.0 7.748 0.200 1.1137 14.800 111.350 0.928 9.285 6.946 69.458
11.0 8.523 0.220 1.1250 16.110 123.730 1.032 9.379 7.718 70.164
12.0 9.298 0.240 1.1363 17.390 136.340 1.137 9.474 8.505 70.870
13.0 10.080 0.260 1.1476 18.650 149.170 1.244 9.568 9.305 71.575
14.0 10.850 0.280 1.1589 19.880 162.220 1.353 9.662 10.120 72.279
15.0 11.630 0.300 1.1702 21.090 175.500 1.464 9.756 10.950 72.983
16.0 12.400 0.320 1.1815 22.270 189.000 1.576 9.850 11.790 73.685
17.0 13.180 0.340 1.1927 23.430 202.730 1.691 9.944 12.650 74.387
18.0 13.950 0.360 1.2040 24.560 216.680 1.807 10.040 13.520 75.088
19.0 14.730 0.380 1.2152 25.670 230.840 1.925 10.140 14.400 75.787
20.0 15.500 0.400 1.2263 26.760 245.230 2.045 10.230 15.300 76.485
21.0 16.280 0.420 1.2375 27.830 259.830 2.167 10.320 16.210 77.180
22.0 17.050 0.440 1.2486 28.870 274.650 2.291 10.410 17.140 77.874
23.0 17.830 0.460 1.2597 29.900 289.690 2.416 10.510 18.080 78.566
24.0 18.600 0.480 1.2708 30.900 304.930 2.543 10.600 19.030 79.255
25.0 19.370 0.500 1.2818 31.880 320.400 2.672 10.690 19.990 79.943
26.0 20.150 0.520 1.2928 32.840 336.070 2.803 10.780 20.970 80.628
27.0 20.920 0.540 1.3037 33.780 351.940 2.935 10.870 21.960 81.310
28.0 21.700 0.560 1.3146 34.700 368.020 3.069 10.960 22.960 81.988
29.0 22.470 0.580 1.3254 35.600 384.310 3.205 11.050 23.980 82.665
30.0 23.250 0.600 1.3362 36.490 400.800 3.342 11.140 25.010 83.338
31.0 24.020 0.620 1.3470 37.350 417.490 3.482 11.230 26.050 84.007
32.0 24.800 0.640 1.3576 38.200 434.370 3.622 11.320 27.100 84.673
33.0 25.570 0.660 1.3683 39.030 451.450 3.765 11.410 28.170 85.335
34.0 26.350 0.680 1.3788 39.840 468.720 3.909 11.500 29.240 85.994
35.0 27.120 0.700 1.3893 40.630 486.170 4.054 11.590 30.330 86.648
36.0 27.900 0.720 1.3997 41.410 503.820 4.201 11.670 31.430 87.299
37.0 28.670 0.740 1.4101 42.170 521.640 4.350 11.760 32.540 87.944
38.0 29.450 0.760 1.4204 42.920 539.650 4.500 11.850 33.670 88.586
39.0 30.220 0.780 1.4306 43.640 557.830 4.652 11.930 34.800 89.223
40.0 31.000 0.800 1.4407 44.360 576.190 4.805 12.020 35.950 89.854
41.0 31.770 0.820 1.4508 45.050 594.710 4.959 12.100 37.100 90.481
42.0 32.550 0.840 1.4607 45.740 613.400 5.115 12.180 38.270 91.103
43.0 33.320 0.860 1.4706 46.400 632.260 5.272 12.270 39.440 91.720
44.0 34.100 0.880 1.4804 47.060 651.270 5.431 12.350 40.630 92.330
45.0 34.870 0.900 1.4901 47.690 670.440 5.591 12.430 41.830 92.935
46.0 35.650 0.920 1.4997 48.320 689.760 5.752 12.510 43.030 93.535
47.0 36.420 0.940 1.5092 48.930 709.220 5.914 12.590 44.250 94.129
48.0 37.200 0.960 1.5187 49.520 728.830 6.078 12.670 45.470 94.716
49.0 37.970 0.980 1.5280 50.100 748.580 6.242 12.740 46.700 95.297
50.0 38.740 1.000 1.5372 50.670 768.460 6.408 12.820 47.940 95.872
51.0 39.520 1.000 1.5506 51.490 790.690 6.594 12.930 49.330 96.711
52.0 40.290 1.000 1.5604 52.070 811.250 6.765 13.010 50.610 97.317
 Technical
Data 19 of 44

Table 3 Specific Heats of Caustic Soda Solutions in BTU’s per Pound

PERCENT TEMPERATURE °F
CAUSTIC 32 40 50 60 80 100 120 140 160 180 200 220 240 260 280 300

0 1.004 1.003 1.001 0.999 0.998 0.997 0.998 0.999 1.000 1.002 1.004 - - - - -
2 0.965 0.967 0.968 0.969 0.972 0.974 0.977 0.978 0.980 0.983 0.986 - - - - -
4 0.936 0.940 0.943 0.946 0.951 0.954 0.957 0.960 0.962 0.965 0.966 - - - - -
6 0.914 0.920 0.924 0.928 0.933 0.938 0.941 0.944 0.946 0.948 0.950 - - - - -
8 0.897 0.902 0.907 0.911 0.918 0.923 0.927 0.930 0.932 0.934 0.936 - - - - -
10 0.882 0.888 0.893 0.897 0.905 0.911 0.916 0.918 0.920 0.922 0.923 - - - - -
12 0.870 0.877 0.883 0.887 0.894 0.901 0.906 0.909 0.911 0.912 0.913 - - - - -
14 0.861 0.868 0.874 0.879 0.886 0.892 0.897 0.901 0.903 0.903 0.904 - - - - -
16 0.853 0.860 0.866 0.871 0.880 0.886 0.891 0.894 0.896 0.897 0.897 - - - - -
18 0.847 0.854 0.860 0.865 0.873 0.880 0.885 0.888 0.890 0.891 0.891 - - - - -
20 0.842 0.848 0.854 0.859 0.868 0.875 0.880 0.884 0.886 0.886 0.887 - - - - -
22 0.837 0.844 0.849 0.854 0.863 0.870 0.876 0.880 0.882 0.882 0.883 - - - - -
24 - 0.839 0.844 0.849 0.858 0.866 0.873 0.877 0.879 0.879 0.880 - - - - -
26 - 0.835 0.840 0.845 0.854 0.863 0.869 0.874 0.875 0.876 0.876 - - - - -
28 - 0.830 0.836 0.841 0.850 0.859 0.866 0.870 0.872 0.872 0.873 - - - - -
30 - 0.826 0.832 0.837 0.846 0.855 0.862 0.866 0.868 0.869 0.869 - - - - -
32 - 0.822 0.828 0.833 0.842 0.850 0.857 0.862 0.863 0.864 0.864 - - - - -
34 - - 0.823 0.828 0.837 0.845 0.852 0.856 0.857 0.858 0.858 - - - - -
36 - - 0.819 0.824 0.832 0.840 0.845 0.849 0.850 0.851 0.851 - - - - -
38 - - 0.816 0.820 0.827 0.833 0.837 0.841 0.842 0.842 0.843 - - - - -
40 - - 0.812 0.815 0.821 0.826 0.829 0.831 0.832 0.832 0.832 - - - - -
42 - - 0.807 0.809 0.813 0.816 0.819 0.819 0.820 0.820 0.820 - - - - -
44 - - - 0.802 0.804 0.806 0.807 0.807 0.807 0.806 0.804 - - - - -
46 - - - 0.793 0.794 0.795 0.794 0.794 0.793 0.791 0.789 - - - - -
48 - - - - 0.783 0.782 0.781 0.780 0.779 0.777 0.776 - - - - -
50 - - - - 0.771 0.769 0.768 0.767 0.765 0.765 0.764 0.763 0.762 0.762 0.761 0.761
52 - - - - 0.759 0.757 0.756 0.754 0.753 0.752 0.751 0.749 0.748 0.747 0.746 0.745
54 - - - - 0.746 0.744 0.741 0.739 0.739 0.738 0.737 0.735 0.733 0.731 0.730 0.728
56 - - - - 0.733 0.730 0.728 0.726 0.724 0.723 0.722 0.721 0.719 0.717 0.715 0.713
58 - - - - - 0.719 0.717 0.715 0.713 0.711 0.709 0.707 0.705 0.703 0.702 0.700
60 - - - - - 0.706 0.705 0.703 0.701 0.699 0.697 0.696 0.693 0.691 0.690 0.688
62 - - - - - - 0.694 0.692 0.690 0.688 0.687 0.685 0.683 0.681 0.679 0.677
64 - - - - - - 0.684 0.682 0.681 0.679 0.677 0.675 0.673 0.671 0.670 0.668
66 - - - - - - 0.675 0.673 0.671 0.669 0.668 0.666 0.664 0.662 0.660 0.658
68 - - - - - - - 0.663 0.662 0.660 0.658 0.656 0.655 0.653 0.651 0.649
70 - - - - - - - 0.655 0.653 0.651 0.649 0.647 0.646 0.644 0.642 0.640
72 - - - - - - - - 0.645 0.643 0.641 0.639 0.637 0.635 0.634 0.632
73 - - - - - - - - - 0.639 0.637 0.635 0.633 0.631 0.630 0.628
74 - - - - - - - - - 0.635 0.633 0.631 0.629 0.628 0.626 0.624
74.5 - - - - - - - - - 0.633 0.631 0.629 0.627 0.626 0.624 0.622
76 - - - - - - - - - 0.628 0.627 0.625 0.623 0.621 0.619 0.617
78 - - - - - - - - - - 0.620 0.618 0.616 0.615 0.613 0.611
 Technical
Data 20 of 44

Properties of Anhydrous Table 6

Enthalpy of
Caustic Soda
Anhydrous Caustic Soda
Table 4
(Above 32°F base temperature)
Miscellaneous Properties
Solid NaOH Molten NaOH
Property Value
Chemical Formula . . . . . . . .NaOH Temp.°F BTU/lb Temp.°F BTU/lb
Molecular Weight . . . . . . . .40.00 32 0.00 605.1 356.06
Freezing or melting
50 5.57 650 381.47
point . . . . . . . . . . . . . . . . . .318°C or 604°F
Boiling point . . . . . . . . . . . .1388°C or 2530°F at 100 21.71 700 408.94
760 mm Hg pressure 150 38.82 750 435.59
Specific heat . . . . . . . . . . . .0.353 cal/gm/°C at 200 56.91 800 461.28
20°C or 0.353 250 75.98 850 486.48
BTU/Ib/°F at 68°F 300 96.01 900 510.70
Free energy of 350 117.03 950 534.12
formation . . . . . . . . . . . . . . .-90,762 cal/mol at 400 139.02 1000 556.72
25°C, 760 mm Hg 450 161.98 1050 578.52
pressure 500 185.92 1100 599.51
Refractive index for
550 210.83 1150 619.68
light wavelength of
5894 A . . . . . . . . . . . . . . . . .N = 1.433 at 320°C 600 281.27 1300 675.35
N = 1.421 at 420°C 605.1 283.97 1350 692.29

Latent heat of fusion . . . . . .40.0 cal/gm or 72.0

BTU/lb
Lattice energy . . . . . . . . . . .176.2 kg-cal/mol Table 7
Entropy . . . . . . . . . . . . . . .12.43 kg-cal/mol/°K Viscosity of
at 25°C, 760 mm Hg
pressure
Molten Caustic Soda
Heat of formation . . . . . . . . 101.723 kcal/mol Temp. °C . . . . . . . . . . . 350 400 450 500 550
Na+1/2O2 +1/2H2 = NaOH Viscosity, centipoise . . . 4.0 2.8 2.2 1.8 1.5

Table 5
Specific Gravity of
Solid Caustic Soda Table 8
Vapor Pressure of
Temp.°C 20 299.6 320 350 400 450 Molten Caustic Soda

Specific Temp.°C . . . . . . . .1000 1050 1100 1200 1300 1388

gravity 2.130 2.08 1.786 1.771 1.746 1.722
Vapor Pressure
in mm Hg . . . . . . . . . .41 66 103 225 447 760
Note:The average bulk density of flake Caustic Soda is
about 60 pounds per cubic foot. This value varies
with the packing conditions and flake
characteristics.
 Technical
Data 21 of 44

Properties of Table 11
Caustic Soda Solutions Heat of Solution of Caustic Soda
Heat Liberated
% Moles H2O/ BTU/lb. BTU/lb. cal/g
NaOH Mole NaOH NaOH Solution NaOH
Table 9 0.44 500 455.8 2.0 253.2
Coefficient of Expansion of 0.55 400 456.0 2.5 253.3
Caustic Soda Solutions 1.10 200 456.6 5.0 253.7
2.17 100 458.3 9.9 254.6
The coefficient of expansion is the volume change 4.26 50 462.0 19.7 256.7
per unit change in temperature. It may be derived 8.16 25 462.6 37.7 257.0
from data on the change of density with tempera- 14.14 13.5 470.1 66.5 261.2
ture according to the following formula: 19.80 9 462.2 91.5 256.8
24.10 7 457.9 110.4 254.4
d = 1.0200 + 0.0105OX - (0.0005+0.0000049X)t 30.77 5 419.2 129.0 232.9
42.55 3 323.5 137.6 179.7
Note: “d” is the density in g/cc; “X” is the concen-
tration in percent by weight of NaOH; and “t” is the Table 12
temperature in °C. The formula is limited to con- Heat of Dilution of
centrations from 10% to 70% NaOH and to tem- Caustic Soda Solutions
peratures from 15°C to 70°C.
Wt.% BTU/lb BTU/lb
NaOH NaOH Solution
0 0 0
Table 10
2 + 1.18 + 0.0236
Compressibility of
4 - 2.04 - 0.0808
Caustic Soda Solutions 6 - 4.78 - 0.287
8 - 7.15 - 0.572
Moles H2O/ 6 10 - 8.60 - 0.860
Mole NaOH Density B x 10
25.01 1.08670 31.23 12 - 9.13 - 1.09
50.09 1.04391 36.15 14 - 8.65 - 1.21
100.15 1.02114 39.12 16 - 7.34 - 1.17
18 - 4.99 - 0.897
Note: The compressibility coefficient B is 20 - 1.50 - 0.301
expressed as compressibility 22 + 3.28 + 0.721
per cc per megabar at 25°C. 24 9.47 2.27
Data is valid between 100-300 26 17.14 4.46
megabars. 28 26.43 7.40
30 37.34 11.20
32 49.97 15.99
34 64.05 21.76
36 79.63 28.66
38 96.50 36.67
40 114.2 45.69
42 132.8 55.78
44 151.7 66.76
46 170.7 78.52
48 189.7 91.04
Note: Enthalpy of solutions at 68°F relative to
infinitely dilute solutions.
 Technical
Data 22 of 44

Table 13 Table 14

Index of Refraction of Hydrogen Ion Concentrations of

Caustic Soda Solutions Caustic Soda Solutions at 25°C

NaOH NaOH
Temp.°C g/L Refractive Index % NaOH Moles/L pH
20°C 0 1.33302
7.88 1.33517 7.40 2.0 14.0
13.12 1.33660 3.83 1.0 13.8
35.44 1.34236 1.96 0.5 13.6
55.12 1.34714 0.39 0.1 12.9
98.48 1.35685 0.20 0.05 12.6
131.52 1.36364 0.04 0.01 12.0

25°C 0 1.33251 Due to the difficulty of obtaining accurate pH read-

7.88 1.33467 ings at values above 12, pH is not a valid method
13.08 1.33605 to determine concentration.
35.4 1.34174
55.04 1.34644
98.28 1.35603
131.2 1.36279

30°C 0 1.33196
7.88 1.33411
13.04 1.33551
35.36 1.34108
54.96 1.34572
98.08 1.35530
130.92 1.36204
 Technical
Data 23 of 44

Graph 1
Boiling and Solidifying Temperatures of Aqueous Caustic Soda Solutions
 Technical
Data 24 of 44

Graph 2
Specific Gravity of Aqueous Caustic Soda Solutions
 Technical
Data 25 of 44

Graph 3
Viscosity of Aqueous Caustic Soda Solutions
 Technical
Data 26 of 44

Graph 4
Vapor Pressures of Aqueous Caustic Soda Solutions
 Technical
Data 27 of 44

Graph 5
Approximate Resultant Temperature When Diluting Caustic Soda

Note: Graph for use starting with 50% Caustic Soda Solution using 70°F water.
 Technical
Data 28 of 44

Graph 6
Relative Enthalpy of Aqueous Caustic Soda Solutions

To approximate the final temperature after diluting a NaOH

solution, start on the bottom axis at the percentage of the origi-
nal solution. Proceed up until the temperature of the original
solution is reached. From that point, draw a line that intersects
on the y-axis at the temperature of the water used for dilution.
Then find the final diluted percentage on the x-axis and draw a
vertical line that intersects the second line drawn. The intersec-
tion point of those lines represents the resultant temperature.
Example: Diluting 50% NaOH at 120°F to 20% using 80°F water.
* Approximate resultant temperature 143° F

•
 Technical
Data 29 of 44

Graph 7
Solubility of Sodium Chloride in Aqueous Caustic Soda Solutions
 Technical
Data 30 of 44

Graph 8
Thermal Conductivity of Aqueous Caustic Soda Solutions
0.42
190 F

170 F
0.41

130 F

0.4

100 F
Thermal Conductivity - BTU/hr x Sq. Ft x F

0.39

90 F

0.38
70 F

0.37
50 F

0.36

30 F

0.35

0.34

0.33

0.32
0 10 20 30 40 50 60 70 80

Percent NaOH by weight

 Technical
Data 31 of 44

Graph 9
Specific Conductance of Aqueous Caustic Soda Solutions
 Dilution Calculations 32 of 44

HOW TO DILUTE DILUTION GRAPH

CAUSTIC SODA SOLUTIONS
Sometimes it is necessary to dilute caustic soda
before it is used, or when the potential for freezing
exists. A procedure for calculating the amount of
concentrated caustic and water required is given
below.
Graph 10 can also be used to determine approxi-
mate volumes of 50% NaOH and water necessary to
achieve a particular dilution. For example, you want
to produce 3,000 gallons of a 25% NaOH solution
and want to know how much water and 50% NaOH
are needed to accomplish this goal.

DILUTING A SOLUTION Using the chart, start on the bottom axis at the
3,000 gallon line. Proceed upward until you intersect
Problem: To dilute 3,000 gallons of 50% NaOH to
the first 25% line on the bottom half of the graph.
a 20% solution. How much water is necessary to
From the intersection point go to the right and left
accomplish this task?
axes to determine the volume and weight of water
needed. In this case the volume is read at 1,920 gal-
Solution: The dilution can be simplified by using
lons and the weight at 16,000 pounds.
the following formula:
D=V[A(B-C)/C]
Then continue upward until you intersect the 25%
line at the top of the graph. Again from the intersec-
Where:
tion point go to the left and right axes to determine
A=Specific gravity of strong solution
the volume and weight of 50% NaOH needed. In this
B=Concentration of strong solution (% NaOH)
case the volume is read at 1,248 gallons and the
C=Concentration of desired solution(% NaOH)
weight at 16,000 pounds.
D=Volume of water to be added
V=Volume of strong solution
Therefore, it would take 1,248 gallons of 50%
(The specific gravity of 50% NaOH is 1.5372 taken
NaOH to be added to 1,920 gallons of water to pro-
from Table 2)
duce 3,000 gallons of a 25% solution.
Therefore:
D=3,000((1.5372)(50-20)/20)
D=3,000(2.3058)=6,917 gallons
Result: It will take 6,917 gallons of water to dilute
3,000 gallons of 50% NaOH to a 20% solution.

VOLUME OF FINAL SOLUTION

It should be noted that when diluting caustic soda,
volumes are not additive. Therefore, in the previous
example, the final volume of the solution would not
be 6,917 gallons of water + 3,000 gallons of 50%
NaOH = 9,917 total gallons. The actual volume will
be slightly less. To calculate the final volume, the
water and caustic soda must be converted to a
weight basis, and then divided by the density of the
desired solution.
 Dilution
Calculations 33 of 44

Graph 10
Approximate Dilution Chart For 50% Caustic Soda

DETERMINATION OF
THE TOTAL
ALKALINITY OF
CAUSTIC SODA
PURPOSE AND THEORY
The accurate determination of
the total alkalinity value for caustic
soda is necessary for calculating
the correct billing concentrations of
this product.
Total alkalinity in caustic soda
products is determined by titration
of a sample with a standardized
solution of 1N hydrochloric acid.
Modified methyl orange indicator is
used to determine the titration
endpoint.
This procedure is based on ASTM
E291-04, Standard Test Methods
for Chemical Analysis of Caustic
Soda and Caustic Potash, sections
8 through 14.
APPARATUS
100 ml Buret; Class A
Volumetric, Fisher Scientific Cat #:
03-775 or equivalent.
Analytical Balance; capable of
weighing to 0.001 grams.
250 ml Erlenmeyer Flasks; wide
mouth, Fisher Cat#: 10-090B or
equivalent.
Magnetic Stirrer; Fisher Cat#:
14-493-120S or equivalent.
Magnetic stirring bars; 1 1/2” x
5/16” dia. Fisher Cat#: 14-511-64
or equivalent.
REAGENTS
1N Hydrochloric Acid;
measure 83.0 ml of ACS Reagent
grade concentrated hydrochloric
acid into a graduated cylinder and
transfer it to a one liter volumetric
flask containing approximately 500
ml of deionized water. Dilute to vol-
ume with additional water, mix well
and store in a tightly closed con-
tainer. A prepared solution of 1N
Methods
of Analysis
HCl can also be purchased (Fisher
Scientific Cat# SA48-20 or equiva-
lent). Hydrochloric Acid must be
standardized to ±0.0001N before
use.
Sodium Carbonate;
anhydrous, volumetric grade (EM
Science Cat#: 6394-2 or equiva-
lent.) Dry at 250°C in a platinum or
porcelain crucible for 4 hours. Store
in a desiccator.
Modified methyl orange
indicator; dissolve 0.14 grams of
methyl orange (Fisher Cat#: M216-
25) and 0.12 grams of Xylene
Cyanole FF (Fisher Cat#: BP565-
10) in deionized water and dilute to
100 ml.
Water, Deionized & Carbon
Dioxide free; boil and cool the
deionized water or purge it with
nitrogen for two hours.
SAFETY
Refer to the MSDS for the proper
handling procedures for each of the
chemicals listed in this procedure.
Caustic soda is a strong base.
Hydrochloric acid is a strong
acid. These chemicals are corro-
sive to body tissue and can
cause immediate and severe
burns to eyes. Wear proper
gloves, proper eye protection
and other protective clothing
when handling these chemicals.
PROCEDURE
A. STANDARDIZATION OF 1N
HYDROCHLORIC ACID
1. Weigh 4.2 grams of sodium
carbonate to the nearest
0.0001 gram into a weighing
dish. Carefully transfer to
an Erlenmeyer flask. Add 75
ml of deionized water and
swirl to dissolve. Add three
drops of the modified methyl
orange indicator and titrate
34 of 44
with the HCl solution to a
steel gray color change.
2. The following formula is used
to calculate the normality of
the HCl.
Let:
N = Normality of HCl
W = Weight (g) of Na2CO3
used
V = Volume (ml) of HCl
required to endpoint.
Milliequivalent weight of
Na2CO3= 0.053
N = W/V x 0.053
3. Determine the normality by
averaging the result of at
least three titrations.
B. ANALYSIS
1. To a clean, dry Erlenmeyer
flask, accurately weigh, to the
nearest 0.001 grams, 6 to 7
grams of 50% NaOH. Weighing
should be performed as rapidly
as possible.
2. Immediately add 50 ml of deion-
ized water, making sure the
sides of the beaker are washed
down.
3. Add 3 to 4 drops of modified
methyl orange indicator and
carefully add the magnetic stir-
ring bar.
4. Titrate the sample to a steel
gray color with 1N HCl. Samples
should be titrated as soon as
possible to avoid pick up of car-
bon dioxide from the air.
5. Record the volume of acid
required to reach this color.
Estimate the buret reading to
the nearest 0.02 ml.

C. CALCULATIONS
The following are formulas used
to calculate total alkalinity.
Let:
W = Weight (g) of sample titrated
N = Normality of HCl
V = Volume (ml) of HCl required
Milliequivalent wt. of Na2O =
0.03099
% Na2O = (V) (N) (0.03099)(100)
W point. The results are reported as
% NaOH = 1.2907 (%Na2O)
EXAMPLE
6.530 grams of caustic soda
required the addition of 81.77 ml of
1.0011N HCl to reach the modified
methyl orange endpoint.
% Na2O = (V) (N) (0.03099)(100)
W of carbonate. It has been found
% Na2O = (81.77)(1.0011)(3.099)
6.530
% Na2O = 38.85%
% NaOH = (1.2907) (38.85)
% NaOH = 50.14%
QUALITY ASSURANCE
With each batch of samples
being analyzed, at least one of the
samples should be analyzed in
duplicate. On a regular basis, sam-
ples that have been previously
analyzed for total alkalinity should
be reanalyzed and the results com-
pared.
Alkalinity values obtained for
each sample should be compared
with OxyChem specifications for
that product. Hydrochloric acid
should be restandardized at least
monthly.
Methods
of Analysis
DETERMINATION OF
SODIUM HYDROXIDE
IN CAUSTIC SODA
PURPOSE AND THEORY
The sodium hydroxide content of
caustic soda is determined by
adding barium chloride to a pre-
pared sample and titrating with 1 N
HCl to the phenolphthalein end
percent NaOH on a sample weight
basis.
Even with the utmost care, the sep-
arate determination of total alkalini-
ty (previous method) and hydroxide
alkalinity often provides significant
differences. This difference is then
typically attributed to the presence
that separate titrations for total
alkalinity and hydroxide alkalinity,
or dual end-point titrations that
attempt to quantify total and
hydroxide alkalinity in a single pro-
cedure, often provide results for
carbonate that are many times
higher than the actual carbonate
content of the material.
Although the method for hydrox-
ide alkalinity is included here,
because the usual carbonate con-
tent of caustic soda is very low, we
suggest the use of the method for
total alkalinity alone. The carbonate
content is typically as low as or
lower than the measurement error
inherent in the analytical methods.
As an alternative, we suggest the
use of the method for total alkalini-
ty, the method for sodium carbon-
ate determination (next method in
this handbook), and a calculation
for hydroxide alkalinity as shown in
ASTM E291-04, Standard Test
Methods for Chemical Analysis of
Caustic Soda and Caustic Potash,
section 12.
35 of 44
APPARATUS
100 ml Buret; Class A
Volumetric, Fisher Scientific Cat #:
03-775 or equivalent.
Analytical Balance; capable of
weighing to 0.001 grams.
250 ml Erlenmeyer Flasks; wide
mouth, Fisher Cat#:10-090B or
equivalent.
Magnetic Stirrer; Fisher Cat#: 14-
493-120S or equivalent.
Magnetic stirring bars; 1-1/2” x
5/16” dia. Fisher Cat#: 14-511-64
or equivalent.
REAGENTS
1N Hydrochloric Acid; the
preparation of this reagent is
described in the method for:
“Determination of Total Alkalinity”.
1% Phenolphthalein Indicator;
dissolve one gram of phenolph-
thalein (Aldrich Cat#: 10,594-5 or
equivalent) in 100 ml of methanol.
10% Barium Chloride; Dissolve
120 g of reagent grade BaCl2.2H2O
(Fisher Cat#: B34-500) in 880 ml of
deionized water.
Water, Deionized & Carbon
Dioxide free; boil and cool the
deionized water or purge it with
nitrogen for two hours.
SAFETY
Refer to the MSDS for the
proper handling procedures for
each of the chemicals listed in
this procedure. Caustic soda is a
strong base. Hydrochloric acid
is a strong acid. These chemi-
cals are corrosive to body tissue
and can cause immediate and
severe burns to eyes. Wear
proper gloves, proper eye pro-
tection and other protective
clothing when handling these
chemicals. Barium chloride is
highly toxic. Avoid inhaling bari-
um chloride dust.

PROCEDURE
A. STANDARDIZATION OF 1N
HYDROCHLORIC ACID
Standardization procedure is
described in the method for:
“Determination of Total Alkalinity”.
B. ANALYSIS
1. To a clean, dry Erlenmeyer
flask, accurately weigh, to the
nearest 0.001 grams, 6 to 7
grams of 50% NaOH. Weighing
should be performed as rapidly
as possible.
2. Immediately add 100 ml of bari-
um chloride solution, making
sure the sides of the beaker are
washed down.
3. Add 3 to 4 drops of phenolph-
thalein indicator and carefully
add the magnetic stirring bar.
4. Titrate the sample with 1N HCl
until the pink color changes to
water white. The sample should
be titrated as soon as possible
to avoid pick up of carbon diox-
ide from the air.
5. Record the volume of acid
required to reach this color, esti-
mating the buret reading to the
nearest 0.02 ml.
CALCULATIONS
The following are formulas used
to calculate % NaOH.
Let:
W = Weight (g) of sample titrated
N = Normality of HCl
V = Volume (ml) of HCl required
Milliequivalent wt. of NaOH =
0.04000
% NaOH = (V) (N) (0.04000) (100)
Methods
of Analysis
W PURPOSE AND THEORY
EXAMPLE
6.467 grams of caustic soda
required the addition of 80.85 ml of
1.0020N HCl to reach the phe-
nolphthalein endpoint.
% NaOH = (V) (N) (0.04000) (100)
W dioxide evolved. Accurate results
% NaOH = (80.85) (1.0020)(4.000)
6.467
% NaOH = 50.11%
QUALITY ASSURANCE
For each batch of samples being
analyzed, at least one of the sam-
ples should be analyzed in dupli-
cate. On a regular basis, samples
that have been previously analyzed
for total alkalinity should be reana-
lyzed and the results compared.
Alkalinity values obtained for each
sample should be compared with
OxyChem specifications.
Hydrochloric acid should be
restandardized at least monthly.
DETERMINATION OF
SODIUM CARBONATE
IN CAUSTIC SODA
(Gravimetric)
36 of 44
The sodium carbonate
content of a sample of caustic soda
is determined by a direct gravimet-
ric method. The method involves
acidification of the caustic soda
sample with dilute sulfuric acid,
boiling, and weighing the carbon
can be obtained when the sodium
carbonate content is 0.01% or
greater. This method should be
used to analyze samples of liquid
caustic soda containing 0.01% to
0.25% Na2CO3.
This procedure is based on ASTM
E291-04, Standard Test Methods
for Chemical Analysis of Caustic
Soda and Caustic Potash, sections
25 through 33. Although it is includ-
ed as a reference for anyone who
may wish to perform the analysis, it
should be noted that the procedure
is rather lengthy, may show poor
precision and is susceptible to error
because of air intrusion into the
apparatus.
OxyChem typically utilizes a car-
bon analyzer in inorganic mode for
the rapid and precise determination
of carbonate content of caustic
soda. For further information
regarding the carbon analyzer
method, please contact technical
Service.

APPARATUS
See the CO2 train sketch on the
previous page.Air for sweep is
drawn in through “A.” This air must
be scrubbed free of CO2. The
ground-glass jointed tube fitted into
the top of “A” should be packed
with 8-20 mesh ascarite with a
layer of anhydrous granular copper
sulfate on top.
U-tube “D”
Add a few glass beads and 5 to
10 ml of concentrated H2SO4. The
acid takes up the bulk of the mois-
ture passing through condenser “C”
and should be changed often
depending on frequency of use.
U-tube “E”
Pack with dehydrated copper sul-
fate pumice. This packing material
is prepared by soaking pulverized
pumice having the grain size of
wheat in saturated copper sulfate
solution drying at 150 -180oF. The
product must be kept in a well
stoppered bottle.
U-tube “F”
Pack with anhydrous
magnesium perchlorate. This
removes all final traces of
moisture carried through the sys-
tem.
Ascarite - Absorbing Tower “G”
Pack inside tube with 8-20 mesh
ascarite. Over the top layer add
about 0.25 inch of magnesium per-
chlorate and cover with absorbent
cotton. The cotton will prevent loss
of weight due to carry-over of dust
particles. After tower is packed, it
should be hooked into the system
and swept with CO2-free air for a
period of 15 to 20 minutes.
U-tube “H”
Pack with 8-20 mesh ascarite.
Methods
of Analysis
REAGENTS
Sulfuric Acid; 12 N with 27.8 g.
FeSO4.7H2O per liter.
Sulfuric Acid, concentrated.
Ascarite II; 8-20 mesh (sodium hydrox-
ide coated silica.)
Magnesium Perchlorate, anhydrous.
Copper (II) Sulfate, anhydrous.
Water, Deionized & Carbon Dioxide
free; boil and cool the deionized water
or purge it with nitrogen for two hours.
SAFETY
Caustic soda as dust or mist is
intensely irritating to the
respiratory system, skin, and eyes.
Become familiar with the first aid
measures recommended in this
Handbook.
When preparing 12 N sulfuric acid,
the concentrated acid must be
poured slowly into water with con-
stant stirring.
Wear safety glasses with side
shields when handling caustic soda
samples or acid solutions.
PROCEDURE
1. Sample Preparation
50% liquid caustic soda will solidify
at 54oF. If the sample
is solidified at the time of
analysis, it may be thawed out by
placing the container in hot water
until no solids are present. The lip of
the bottle may be wiped before the
sample is poured into a weighing
bottle.
Carbonate and moisture pickup
should be avoided by rapid sample
handling.
In all cases, samples for carbonate
analysis should be the first taken
from the sample bottle to minimize
carbon dioxide pickup from the
atmosphere.
37 of 44
3
2. Analysis
The train must be conditioned
daily before any samples are run.
This is done by making a regular
determination using a sample that
contains carbonate. Following this,
a blank should be run on the train
to make sure that the train is leak
free. This is done by making a reg-
ular determination but omitting the
sample. If the ascarite weighing
tower gains more than 0.2 mg in
weight during the blank run, the
train probably has a leak.
After the train has been condi-
tioned and found to be leak free,
the samples are run as follows:
1. Two absorbing towers (G) must
be conditioned and weighed prior
to analysis. These will be called
G1 and G2 in the procedure. The
use of two towers will enable the
analyst to conserve time when
performing more than one analy-
sis.
2. Weigh a sample of at least 20g.
(50% basis) or large enough to
contain 5 mg of CO2 into a flask
“B” using an analytical balance.
Add 4 or 5 glass beads and 80 ml
of CO2-free deionized water and
immediately place the flask into its
proper position in the train.
3. Add 50 ml of 12 N sulfuric acid to
funnel “A.”
4. Place tared tower G1 between U-
tubes “F” and “H.”
5. Open the system starting at U-
tube “H” and working back to “D.”
6. Open cock on funnel “A” and
allow acid to run into flask “B” and
immediately hook vacuum line to
tube “H.” Adjust the flow of air to 4
bubbles per second through the
tip of the stem of funnel“A.”

7. Apply heat to flask “B” and bring
to a boil. Hold “B” contents to boil-
ing point for 3 minutes and
remove heat.
8. Sweep the system for 20 minutes.
While this is being done, the next
sample can be weighed into
another flask (B), and the beads
and distilled water added. This
flask is then stoppered and set
aside until needed.
9. At the end of 20 minutes, the vac-
uum line is removed,tower G1 is
shut off and removed and tower
G2 placed into position. The cock
on funnel “A” is closed and 50 ml
of 12 N sulfuric acid is again
added to funnel “A.”
10.Flask “B” is removed, the stem of
funnel “A” is washed down with
deionized water and the new sam-
ple is placed into position.
11.Tower G2 is opened and the pro-
cedure is repeated beginning at
Step 6.
12.When G1 is removed from the
train, a period of 20 minutes will
Methods
of Analysis
condition the sample for weighing.
During this 20 minute sweep time,
another sample is prepared and
tower G1 is reweighed in order to
determine the weight of CO2 found
in the first sample. Tower G1 is
then ready for Run No. 3.
CALCULATIONS
Report results as percent Na2CO3
calculated to the nearest 0.01. Let:
W(CO2) = Weight of CO2
evolved
W(S) = Weight of sample
% Na2CO3 = (W(CO2)(2.409)(100)
W(S)
EXAMPLE
If a 25 gram sample were used
and the weight of CO2 absorbed in
tower “G” = 0.0125 grams, then:
% Na2CO3 = (0.0125)(2.409)(100)
25
% Na2CO3 = 0.12%
DETERMINATION OF
SODIUM CHLORIDE IN
CAUSTIC SODA
PURPOSE AND THEORY
Chloride is a contaminant in all
grades of caustic soda. Sodium
chloride is present at <100 ppm in
50% membrane caustic soda and
at approximately 1% in 50%
diaphragm caustic soda. Higher
concentrations of this compound
can have undesirable effects in
many applications of the product.
Consequently, accurate determina-
tion of this impurity is most impor-
tant.
When acid solutions of silver ion
and an alkali thiocyanate are mixed
in the presence of a ferric salt, the
thiocyanate has a selective action
toward silver, resulting in the for-
mation of silver thiocyanate. Any
38 of 44
excess of thiocyanate not required
by the silver reacts with ferric salt
to form reddish-brown ferric thio-
cyanate. This color indicates the
completion of the reaction.
An excess of silver nitrate and
the ferric indicator is added to a
sample of caustic soda that has
been acidified with nitric acid. Any
chloride that is contained in the
sample will react with the silver
nitrate to form a silver chloride pre-
cipitate. The silver nitrate that is
remaining in the sample solution
after this reaction is titrated with a
standardized solution of ammonium
thiocyanate. The equations
involved are:
AgNO3 + NaCl ⇒ AgCl + NaNO3
Excess AgNO3 + NH4CNS ⇒
AgCNS + NH4NO3
6 NH4CNS + Fe2(SO4)3 ⇒
2Fe(CNS)3 + 3(NH4)2SO4
(reddish brown color)
This procedure is based on ASTM
E291-04, Standard Test Methods
for Chemical Analysis of Caustic
Soda and Caustic Potash, sections
34 through 40.
OxyChem typically utilizes tur-
bidimetric determination, potentio-
metric titration (similar to ASTM
E29-104, sections 41 through 48,
with modifications to account for
the low chloride content of mem-
brane grade caustic soda) or ion
chromatography. For further infor-
mation regarding any of these
methodologies, please contact
Technical Service.

APPARATUS
25ml Buret; Class A Volumetric,
Fisher Scientific Cat#:03-724-10A
or equivalent.
20ml Pipet; Class A Volumetric,
Fisher Cat#: 13-650-2N
500ml Erlenmeyer flasks; wide
mouth, Fisher Cat#: 10-090C or
equivalent.
Magnetic stirrer; Fisher Cat#:14-
493-120S or equivalent.
Magnetic stirring bars; 1 1/2” x
5/16” dia, Fisher Cat#: 14-511-64
or equivalent.
Analytical Balance; capable of
weighing to 0.001 grams.
REAGENTS
Water, Deionized.
0.1N Silver Nitrate; accurately
weigh 16.99 grams of ACS
Reagent grade silver nitrate (dried
at 110°C for 1 hr) and transfer to a
1L volumetric flask. Dilute to vol-
ume with deionized water, mix well
and store in a tightly closed amber
container. Silver nitrate and its
aqueous solutions are photode-
composed by light and should be
stored in a dark place.
0.1N Ammonium Thiocyanate;
accurately weigh 7.612 grams of
ACS Reagent grade ammonium
thiocyanate and transfer to a one
volumetric flask. Dilute to volume
with deionized water, mix well and
store in a tightly stoppered glass
bottle. The thiocyanate solution
must be standardized to within
±0.0001N prior to use.
Ferric Indicator; prepare a satu-
rated aqueous solution of ferric
ammonium sulfate [FeNH4(SO4)2],
Aldrich Cat# 22,126-0 or equiva-
lent.
1% Phenolphthalein Indicator;
dissolve one gram of phenolph-
thalein (Aldrich Cat#: 10,594-5 or
equivalent) in 100 ml of methanol.
Nitric Acid, 1:1 (v/v); slowly pour
500 ml of ACS Reagent grade nitric
acid in 500 ml of deionized water
as it is stirring. Allow the solution to
cool.
Methods
of Analysis
SAFETY
Refer to the MSDS for the
proper handling procedures for
each of the chemicals listed in
this method.
Caustic soda is a strong base
and nitric acid is a strong acid.
These chemicals are corrosive
to body tissue and can cause
immediate and severe burns to
eyes. Wear proper gloves, prop-
er eye protection and other pro-
tective clothing when handling
these chemicals.
Silver Nitrate is a strong
oxidizing agent. Wear rubber
gloves when handling. Contact
with skin causes a black discol-
oration. Keep away from heat,
sparks and open flames.
PROCEDURE
A. STANDARDIZATION OF
0.1N SILVER NITRATE
Since this procedure determines
the chloride content of a sample by
comparing the amount of unreacted
silver nitrate remaining in a sample
with the amount that is remaining
in a reagent blank, the exact nor-
mality of the silver nitrate need not
be known. If a reagent blank is not
used, silver nitrate standardization
is essential. A manual titration
method is described in “ASTM
Standard Practice for Preparation,
Standardization and Storage of
Standard Solutions for Chemical
Analysis”, Vol 15.05; E200-91, 44-
48.
39 of 44
B. STANDARDIZATION OF
0.1N AMMONIUM
THIOCYANATE
1. Use a volumetric pipet to transfer
20.00 ml of freshly standardized
0.1 N silver nitrate into a 250 ml
Erlenmeyer flask containing 50
ml deionized water, 5 ml of 1:1
nitric acid and 1 ml of ferric indi-
cator. Titrate the AgNO3 with the
NH4SCN solution until the first
permanent reddish-brown color
appears and persists after vigor-
ous shaking for 15 seconds.
Record the volume of NH4SCN
required. Repeat the above pro-
cedure on at least three more
solutions of silver nitrate.
2. Use the following formula to cal-
culate the normality of the
ammonium thiocyanate solution:
N1 = (N2)(V2)/(V1)
where:
N1 = Normality of NH4SCN
N2 = Normality of AgNO3
V1 = Volume of NH4SCN
required
V2 = Volume of AgNO3 added
3. Determine the normality by aver-
aging the results of at least three
titrations.
C. PROCEDURE
1. To a clean dry Erlenmeyer flask,
accurately weigh, to the nearest
0.001 g for smaller samples and
0.01 g for larger samples, an
amount of product as determined
in the following table. Weighing
should be performed as rapidly
as possible.
SAMPLE SIZE FOR CHLORIDE
ANALYSIS
Product Sample size
50% Diaphragm
grade caustic soda . . . . . . . . . .6 g
50% Membrane
grade caustic soda . . . . . . . . .80 g

2. Immediately add 100 ml of
deionized water, making sure the
sides of the beaker are washed
down.
3. Add 2 drops of 1% phenolph-
thalein indicator and carefully
neutralize the sample with 1:1
nitric acid. Caution: The sample
solutions generate consider-
able heat when being neutral-
ized with acid. The flask
should be continuously cooled
in an ice bath while the acid is
slowly added. After the phe-
nolphthalein endpoint has
been reached (color changes
from pink to colorless), add an
additional 5.0 ml of acid.
4. Allow the solution to cool to room
temperature and add a stirring
bar to the flask.
5. Using a volumetric pipet add
20.00 ml of 0.1N silver nitrate,
also add approximately 1 ml of
the ferric indicator solution (see
Note 1).
6. Prepare a reagent blank by
adding two drops of phenolph-
thalein, 5ml nitric acid, 20.00 ml
silver nitrate solution and 1ml of
ferric indicator to a flask contain-
ing 100 ml of deionized water
and a stirring bar.
7. Place the flask containing the
reagent blank on a magnetic stir-
rer and titrate the solution with
0.1N ammonium thiocyanate
until a reddish-brown color per-
sists for at least 15 seconds (see
Note 2). Record the volume of
NH4SCN required to reach the
color change.
8. Titrate the sample solution with
0.1N ammonium thiocyanate
until the same color change is
reached and record the volume
of NH4SCN (see Notes 3 and 4).
Methods
of Analysis
D. CALCULATIONS
The following is the formula
used to calculate the percent chlo-
ride in the sample.
Let:
W = Weight of sample titrated
N = Normality of NH4SCN
V1= Volume of NH4SCN
required to titrate blank
V2= Volume of NH4SCN
required to titrate sample
Milliequivalent wt. of Cl =
0.03545
% Cl = (V1-V2)(N)(0.03545)(100)
W cipitates so they can react with
Calculate the percentage of sodi-
um chloride as follows:
%NaCl = (%Cl)(1.6485)
EXAMPLE
79.28 grams of 50% Membrane
grade caustic soda required the
addition of 19.54 ml of 0.1005 N
NH4SCN to reach the titration end-
point while the reagent blank
required 19.95 ml of NH4SCN to
reach the same endpoint.
% Cl = (V1-V2)(N)(0.03545)(100)
W ride greater than 0.01%, it is
= (19.95-19.54)(0.1005)(3.545)
79.28
% Cl = 0.00180
% NaCl = (% Cl)(1.6485)
% NaCl = (0.00180)(1.6485)
% NaCl = 0.0030% or 30 ppm
NOTES
1. Sample solutions should be
titrated within several minutes of
adding the silver nitrate. The sil-
ver chloride has a tendency to
decompose with exposure to
light giving the solution a pur-
plish color. This color can inter-
40 of 44
fere with an accurate determina-
tion of the endpoint color
change.
2. From the outset of the back-titra-
tion with ammonium thiocyanate,
an appreciable quantity of silver
ions are absorbed on the sur-
face of the precipitates. Because
of this, there is a tendency for a
premature appearance of the
endpoint color. Vigorous stirring
or shaking of the solution is
essential to bring about desorp-
tion of silver ions from the pre-
the thiocyanate.
3. As the endpoint is approached,
increasing amounts of silver
thiocyanate precipitating out of
solution will actually increase the
solubility of silver chloride. Silver
chloride that has precipitated will
redissolve, allowing additional
silver ions to react with the thio-
cyanate. This causes a fading
endpoint and results in low chlo-
ride values. For samples con-
taining concentrations of chlo-
advisable to filter the sample
solution through semi-quantita-
tive paper after the addition of
silver nitrate but prior to titration
with thiocyanate. Removing
most of this precipitate will
greatly decrease the amount of
silver that can be redissolved
during the titration.
4. The white precipitate of silver
thiocyanate interferes with
observation of the color change
at the titration endpoint. It is
sometimes helpful to stop the
stirring or shaking of the sample
and allow the precipitate to set-
tle, in order to observe the color
of the sample solution. If it is
determined during this observa-
tion that the endpoint has not yet
been reached, resume vigorous
stirring before addition of more
NH4SCN.

QUALITY ASSURANCE
Because of difficulties in deter-
mining the exact endpoint when
using this method, only skilled lab-
oratory personnel should attempt to
perform these titrations.
On a regular basis, samples that
have been previously analyzed for
chloride content should be reana-
lyzed and the results compared.
Chloride values should be
checked against OxyChem specifi-
cations.
DETERMINATION OF
IRON IN CAUSTIC
SODA
PURPOSE AND THEORY
Iron can result from contamina-
tion during storage or transport of
the product. Since iron is often
detrimental to the end use of the
product, accurate quantitation of
this element is essential.
Caustic soda is neutralized with
hydrochloric acid and the resulting
solution buffered with sodium
acetate. Hydroxylamine hydrochlo-
ride reduces any iron present in the
ferric state to the ferrous state. o-
phenanthroline (1,10-phenanthro-
line) forms an orange-red complex
with ferrous iron. The intensity of
the color is proportional to the
amount of iron present. By measur-
ing the color intensity with a spec-
trophotometer, the concentration of
iron in a sample of caustic soda
can be determined.
This procedure is based on
ASTM E291-04, Standard Test
Methods for Chemical Analysis of
Caustic Soda and Caustic Potash,
Sections 58 through 66.
Methods
of Analysis
APPARATUS
Visible Spectrophotometer: able
to measure absorbance or percent
transmittance at 510 nanometers.
Analytical Balance: capable of
reading to 0.01 grams.
Volumetric Flask, 1 l, class A:
Fisher catalog # 10-210-8G or
equivalent
Volumetric Flask, 100 ml, class A:
Fisher catalog # 10-210-8C or
equivalent
Pipets, Volumetric, Class A:
1 ml - Fisher catalog #
13-650B or equivalent
2 ml - Fisher catalog #
13-650C or equivalent
5 ml - Fisher catalog #
13-650F or equivalent
10 ml - Fisher catalog #
13-650L or equivalent
15 ml - Fisher catalog #
13-650M or equivalent
Indicator Paper, Hydrion, pH 3.0
to 5.5: Fisher catalog # 14-853-70
or equivalent)
Disposable plastic pipets
("Dispo-pipet")
Cuvettes, quartz: appropriate to
the spectrophotometer in use, 25
mm diameter is typical but other
path lengths providing detection
limits suitable for the user are
acceptable
REAGENTS
Deionized Water
Hydrochloric Acid, concentrated:
reagent grade, Fisher catalog #
A144 or equivalent
Sodium Acetate, 164 grams per
liter: weigh 164.0 (+/- 0.1) grams of
sodium acetate, Fisher catalog #
S210-500 or equivalent, dissolve
and dilute to 1 liter with deionized
water in a 1 liter volumetric flask
41 of 44
Hydroxylamine Hydrochloride,
100 grams per liter: weigh 100.0
(+/- 0.1) grams of hydroxylamine
hydrochloride, Fisher catalog #
H330-500 or equivalent, dissolve
and dilute to 1 liter with deionized
water in a 1 liter volumetric flask
o-phenanthroline, 0.25 %: weigh
2.50 (+/- 0.05) grams of o-phenan-
throline monohydrate, Fisher cata-
log # P70-10 or equivalent, dis-
solve and dilute to 1 liter with
deionized water in a 1 liter volu-
metric flask
1000 μg/ml Iron Standard, suit-
able for ICP/AA, Spex standard
available from Fisher as catalog #
PLFE2-2Y or equivalent
SAFETY
Refer to the MSDS for the
proper handling procedures for
each of the chemicals listed in
this procedure.
Caustic soda is a strong base.
Hydrochloric acid is a strong
acid. The Iron Reference
Solution is acidified with HCl. All
of these chemicals are corrosive
to body tissue and can cause
immediate and severe burns to
eyes. Wear proper gloves, prop-
er eye protection and other pro-
tective clothing when handling
these materials.
Refer to instrument manual for
the proper use of equipment
described in this method.
PROCEDURE
A. SAMPLE ANALYSIS
1. Weigh the appropriate sample,
based on the table below, into a
clean 100 ml volumetric flask.
Record the sample weight.
50% diaphragm grade caustic soda
5-10 g
50% membrane grade caustic
soda 15-20 g
2. Add deionized water to the flask,
such that the flask is slightly less
than half-full, and swirl to mix the
solution.

3. SLOWLY and CAREFULLY, add
concentrated hydrochloric acid to
the flask while constantly swirling
the flask. Continue to add until
the solution is just acidic. Check
the pH by dipping a clean glass
rod into the flask and touching
the rod to the pH indicator paper.
If acidic, the paper will turn red.
If it is still basic, the paper will be
blue. (If another type of indicator
paper is used, verify the appro-
priate colors for the paper you
are using.)
CAUTION:This is a reaction
involving a strong base and a
strong acid. Be sure to add the
acid slowly and to maintain
swirling so that spattering does
not occur. The solution and flask
will become quite warm. Cool
the flask in an ice bath or under
cold running water if desired.
4. If additional samples are to be
analyzed, repeat steps 1 to 3
above for each sample.
5. Prepare a blank by adding about
40 mls of deionized water and
about 2 mls of concentrated
hydrochloric acid to a separate,
clean 100 ml volumetric flask.
6. Using a dispo-pipet, add suffi-
cient sodium acetate solution to
the flasks (the samples and the
blank) to buffer the solution to
pH 3.5 +/- 0.5 pH units. Check
the pH by dipping a clean glass
rod into the flask and touching
the rod to the pH indicator paper.
At the proper pH, the paper will
have a light green color. (If
another type of indicator paper is
used, verify the appropriate color
for the paper you are using.)
7. Pipet 5 mls of hydroxylamine
hydrochloride solution to each
flask.
8. Pipet 5 mls of o-phenanthroline
solution to each flask.
9. Fill the flasks to volume with
deionized water and shake well
Methods
of Analysis
to mix. Allow a minimum of 15
minutes for color development
but complete the reading of the
samples within 30 minutes.
10. Rinse a clean cuvette twice
with small portions of the blank
solution. Then fill the cuvette
with the blank solution. Assure
that there are no bubbles pre-
sent and wipe off the outside of
the cuvette with a soft, lint-free
tissue. Place the cuvette into the
spectrophotometer and zero the
instrument at 0 (zero)
absorbance (A) or 100% trans-
mittance (T). Operate the spec-
trophotometer as directed in your
instrument manual. Remove the
cuvette from the instrument.
11. Fill a cuvette with the sample
solution and load it into the spec-
trophotometer in the same fash-
ion as described in step 9 above.
Record the instrument reading
as either A or T, depending upon
how your calibration curve was
constructed. (See section C
below.)
B. QUALITY CONTROL
1. Perform a duplicate analysis with
each batch of samples. Simply
repeat the Sample Analysis in
section A above using an addi-
tional aliquot of a sample. If
large numbers of samples are
tested, it is suggested that a
duplicate analysis is performed
on one of every ten samples.
2. Perform a sample spike analysis
with each batch of samples. To
do so, prepare a second aliquot
of a sample as directed in steps
1 and 2 of the Sample Analysis
in section A above. Then pipet 2
mls of the 10 μg/ml iron stock
standard (see step 1 in section C
below) into the flask. Complete
the sample preparation as
described in the remaining steps
of section A. This procedure
provides about a 1 (one) μg/g (1
ppm) spike for membrane caus-
tic soda or about a 2 to 4 μg/g (2
42 of 44
to 4 ppm) spike for diaphragm
caustic soda. Different spike lev-
els may be obtained by adding
more or less of the iron stock
standard or using different iron
concentration solutions.
3. The relative percent difference
between duplicates should be no
more than 20%.
4. The spike recovery should be in
the 80% to 120% range.
C. SPECTROPHOTOMETER
CALIBRATION
1. Prepare a stock 10 μg/ml iron
standard by pipetting 1 ml of the
1000 μg/ml iron standard to a
100 ml volumetric flask and dilut-
ing to volume with deionized
water.
2. Obtain six 100 ml volumetric
flasks and label them as 'Blank',
'10 μg', '20 μg', '50 μg', '100 μg'
and '150 μg'. To each of these,
add about 25 mls of deionized
water and 2 mls of concentrated
hydrochloric acid.
3. Pipet 1 ml of the 10 μg/ml iron
stock standard (prepared in step
1 above) to the flask labeled '10
μg'. Similarly, pipet 2 mls of the
iron stock to the flask labeled '20
μg', 5 mls to the flask labeled '50
μg', 10 mls to the flask labeled
'100 μg', and 15 mls to the flask
labeled '150 μg'.
4. Complete the preparation and
reading of the standards by fol-
lowing steps 6 through 11 in sec-
tion A above.
5. Many spectrophotometers will
allow storing the calibration
curve directly on the instrument.
If this is not the case, you may
wish to use a least squares
regression analysis to store the

calibration on a calculator or PC
program. Finally, calibration
curves may be drawn manually
using normal graph paper if plot-
ting concentration vs.
absorbance (A) or semi-log
paper if plotting concentration
(linear axis) vs. transmittance (T
- log axis).
CALCULATION
Calculate the ppm iron by dividing
the micrograms of iron found
from the calibration curve (C) by
the sample weight (W):
ppm Fe = C / W
Methods
of Analysis
DETERMINATION OF
OTHER ELEMENTS IN
CAUSTIC SODA
OxyChem typically utilizes
Inductively Coupled Argon Plasma-
Atomic Emission Spectroscopy
(ICAP-AES) for the analysis of met-
als or elements in caustic soda.
For the determination of mercury,
an automated cold vapor atomic
absorption (CVAA) method, based
on EPA Method 245.1 and ASTM
E538, is utilized.
Since the operation of these instru-
ments varies from manufacturer to
manufacturer, a specific method is
not included here. Follow your
instrument manufacturer's instruc-
tions and recommendations for
performing analysis of this type.
43 of 44
IMPORTANT!!!
Regardless of the brand of instru-
ment, it is necessary to keep in
mind that calibration standards
must be similar to the sample
being analyzed if results are to be
considered accurate.
Caustic soda will form a significant
amount of salt when neutralized:
for example, sodium chloride if
neutralized with hydrochloric acid
or sodium nitrate if neutralized with
nitric acid. Since the sample con-
tains a high amount of dissolved
solids, calibration standards must
be prepared in a similar matrix or
sample results will be in error.
One means of addressing this is to
prepare standards containing the
same amount of dissolved salt that
a sample would contain. This
requires obtaining high purity salts,
which can be quite costly. Another
more economical means of accom-
plishing the "matrix match" is to
use calibration by standard addi-
tion.
In general, analytical results
obtained for elements in caustic
soda will be significantly higher
than the actual values if the sam-
ples are analyzed using a calibra-
tion based on "clean" aqueous
standards as might be used for
water analysis.
 Notes 44 of 44

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